Hydrocracking catalysts and processes employing non-zeolitic molecular sieves

ABSTRACT

Hydrocracking processes are disclosed using novel catalysts comprising medium and large pore non-zeolitic molecular sieves selected from novel compositions such as the silicoaluminophosphates of U.S. Pat. No. 4,440,871, preferably in combination with traditional hydrocracking catalysts such as zeolitic aluminosilicates. The products of the instant processes are characterized by higher isoparaffin to n-paraffin ratios.

This application is a continuation-in-part of U.S. application Ser. No.772,924, filed Sept. 5, 1985, now abandoned, which is a division of U.S.application Ser. No. 683,241, filed Dec. 18, 1984, now U.S. Pat. No.4,818,739.

FIELD OF THE INVENTION

The present invention relates to hydrocracking catalysts comprisingnon-zeolitic molecular sieves and to processes employing suchhydrocracking catalysts.

BACKGROUND OF THE INVENTION

The literature of such catalysts and processes is quite extensive.Certain technical areas have been addressed as of particular interest asis readily apparent based on the large numbers of patents on certaintechnical topics, e.g., the use of certain zeolites in hydrocrackingcatalysts. Representative of the patents in this area are those relatingto the use of ZSM-type zeolites in hydrocracking and include: U.S. Pat.No. 3,894,934 (ZSM-5); U.S. Pat. No. 3,871,993 (ZSM-5, ZSM-11, ZSM-12and ZSM-21); U.S. Pat. No. 3,702,886 (ZSM-5); and U.S. Pat. No.3,758,043 (ZSM-5 in combination with zeolite Y) of and U.S. Pat. No.3,972,983 (ZSM-20).

Although the aforementioned patents on the use of ZSM-type zeolites inhydrocracking catalysts are of interest, the use of these zeolites hasnot been of significant commercial interest to date. The commerciallysignificant activity in the hydrocracking area has been for the mostpart directed to further elaboration on the basic hydrocrackingtechnology which has arisen in relation to zeolite Y, as disclosed inU.S. Pat. No. 3,130,007.

The development of hydrocracking catalysts based on a Y-type zeolite hastaken many directions. Illustrative of the various processes which havearisen are those disclosed in the following patents:

U.S. Pat. No. 3,293,192 discloses a "synthetic ultra stable zeoliticaluminosilicate of the Y-type" (See U.S. Pat. No. 3,594,331, whichdiscloses that Z-14HS is zeolite Y.) which has been prepared bycalcining a low alkali metal Y zeolite and successively base exchangingthe calcined product with a base solution containing ammonium or complexamino salts until the alkali content is less than 1 weight percent andthen calcining this product.

Although there has been extensive development of Y-type hydrocrackingcatalysts there has been little development of truly new hydrocrackingcatalysts based on the development of new molecular sieve components.This paradox, the lack of new catalytic materials despite the sizableeconomic interest, is readily understood by an appreciation of the factthat the work horse of the commercial hydrocracking business is zeoliteY. As a result, the patent literature discloses the clear preferencetowards improving zeolite Y.

The existence of zeolite Y and its use as a catalyst for hydrocrackingprocesses is now well accepted if not, in fact, legendary. Still, thestate of the art relating to zeolite Y and its use in hydrocrackingcatalysts has been generally limited to ion-exchange techniques,aluminum extraction techniques, catalyst formulation techniques and tosecondary treatment processes which tend to remove aluminum from zeoliteY.

The instant invention is distinguished from the hydrocracking catalystsand processes of the prior art by employing a novel family ofnon-zeolitic molecular sieves which can be employed in conjunction withthe catalysts traditionally employed in hydrocracking processes. Thesenovel non-zeolitic molecular sieves, when used in combination withtraditional hydrocracking catalysts, are unique in their ability toprovide products with product distributions different from thoseobtained by use of catalysts derived from zeolitic aluminosilicatesalone.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the yield of the light gasoline fraction as afunction of conversion for a reference catalyst (Catalyst A) and acatalyst (Catalyst B) of this invention.

FIG. 2 is similar to FIG. 1 except Catalyst C, according to thisinvention, is depicted. FIG. 3 is a plot of the calculated RON (ResearchOctane Number) of the light gasoline fraction as a function ofconversion for Catalyst A and Catalyst B.

FIG. 4 is similar to FIG. 3 except Catalyst C is depicted.

FIG. 5 is a plot of the yield of the heavy gasoline fraction as afunction of conversion for Catalyst A and Catalyst C.

FIG. 6 is a plot of the yield of the heavy gasoline fraction as afunction of conversion for Catalyst A and Catalyst B.

FIG. 7 is a plot of the iso to normal ratio for C₅ hydrocarbons as afunction of conversion for Catalyst A and Catalyst C.

FIG. 8 is a plot of the iso to normal ratio for C₆ hydrocarbons as afunction of conversion for Catalyst A and Catalyst C.

FIG. 9 is a plot of the iso to normal ratio for C₅ hydrocarbons as afunction of conversion for Catalyst A and Catalyst B.

FIG. 10 is a plot of the iso to normal ratio for C₆ hydrocarbons as afunction of conversion for Catalyst A and Catalyst B.

FIG. 11 is a plot of the iso to normal ratio as a function of carbonnumber for Catalyst A and B.

FIG. 12 is a plot of the C₃ yield as a function of conversion forCatalyst A and Catalyst C.

FIG. 13 is a plot of the C₃ yield as a function of conversion forCatalyst A and Catalyst B.

SUMMARY OF THE INVENTION

The present invention relates to hydrocracking catalysts and tohydrocracking employing such catalysts. The catalysts comprise at leastone non-zeolitic molecular sieve, as hereinafter described, at least onehydrogenation catalyst (noble or base metal) component and ahydrocracking catalyst component, preferably a traditional hydrocrackingcatalyst as heretofore employed and having catalytic activity forhydrocracking hydrocarbon feedstocks at effective hydrocrackingconditions, e.g., particles of a traditional hydrocracking catalystcontaining a zeolitic aluminosilicate(s) of the type generally employedin such hydrocracking catalysts. The non-zeolitic molecular sievesemployed in the instant invention are characterized in their calcinedform by an adsorption of oxygen of at least 4 percent by weight at apartial pressure of 100 torr and a temperature of -186° C., preferablyby an adsorption of isobutane of at least 2 percent by weight at apartial pressure of 500 torr and a temperature of 20° C., and morepreferably, further characterized by an adsorption of triethylamine offrom zero to less than 5 percent by weight at a pressure of 2.6 torr anda temperature of 22° C. as well.

The traditional catalyst component, e.g., a zeolitic aluminosilicate, ischaracterized as being a hydrocracking catalyst component, such asheretofore traditionally employed in hydrocracking processes, e.g., thevarious forms of zeolite Y, silica-alumina, and hydrogenationcomponents. The non-zeolitic molecular sieves employed in this inventionare unique in that they are not zeolitic aluminosilicates (See: ZeoliteMolecular Sieves, by D. W. Breck (1973)), as heretofore employed in theprior art, but are novel non-zeolitic molecular sieves, as hereinafterdescribed.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to hydrocracking processes wherein highboiling hydrocarbon feedstocks are converted to lower boiling productsby cracking the high boiling hydrocarbon feedstock components andhydrogenating unsaturates in the present product. In preferredembodiments, the processes produce gasoline products in higher yieldsand with higher octane numbers than processes using hydrocrackingcatalysts without such non-zeolitic molecular sieve additives.

Hydrocracking processes and the effective conditions for carrying themout are well known in the art. (See, e.g., Zeolite Chemistry andCatalysis, by Jule A. Rabo, ACS Monograph 171, Chapter 13 (1976)).Hydrocracking is known to be of several general types. Two well knowntypes of hydrocracking include the single-stage type and the two-stagetype. In the single-stage type (Unicracking-J.H.C. or JerseyHydrocracking) process the feedstocks are pretreated to removeessentially all sulfur and nitrogen, e.g., by a hydrotreater, wherebydesulfurization and denitrification are effected. The hydrocarbon streamis then hydrocracked in a reactor in the presence of a catalyst at asingle pass conversion of between 40 and 70 percent. Any unconvertedhydrocarbon may be recycled to extinction following scrubbing forammonia removal and fractionation for separation of converted products.The two-stage process (Unicracking-JHC) has been developed whichprovides a second stage that employs the effluent from the single-stagetype hydrocracking process (after passage through an ammonia scrubber)and from a second hydrocracking reactor as the input feed for afractionation unit. The unconverted feedstock is then recycled toextinction in the second hydrocracking reactor. Because the catalyst inthe second hydrocracking reactor operates in an essentially ammonia-freeenvironment the rate of conversion in this reactor can be maintained ata higher level, e.g., 60 to 80 percent and typically is carried out at alower temperature than the first-stage reactor.

It has been found that the use of specific non-zeolitic molecular sievesprovides different product distributions which are more valuablecommercially when such non-zeolitic molecular sieves are employed inconjunction with conventional hydrocracking catalysts (comprising ahydrogenation component and an acid cracking component) having activityat effective hydrocracking conditions. For example, an improvement ingasoline octane of the products, as indicated by an increased ratio ofisoparaffins to normal paraffins, has been observed to occur without aconcurrent decrease in gasoline yield and without an increase in feedconversion when selected non-zeolitic molecular sieves are used incombination with zeolitic aluminosilicate-based hydrocracking catalysts.The isoparaffin to normal paraffin ratio in the gasoline product haslong been employed as an indication of higher octane products and itsincrease or decrease used as an indication of the octane of the gasolineproduct. In the present invention, the increase in high octaneisoparaffins in the light gasoline product (boiling below 185° F.)relative to the normal paraffins occurs without loss in gasoline yieldand feed stock conversion and is of significant commercial importance.This increase in the isoparaffin to normal paraffin ratio in the lightgasoline fraction is particularly significant, since this fraction isnot generally subjected to further processing to improve its octanenumber.

While not wishing to be bound by theory, it is believed that thenon-zeolitic molecular sieve component of the catalysts used in thepresent invention isomerizes normal paraffins in the light gasolinefraction to isoparaffins without contributing significantly to theirconversion by hydrocracking. Thus, these non-zeolitic molecular sievecatalyst additives effect an octane boost without yield loss orincreased conversion of feed. The traditional hydrocracking catalystcomponent of the present invention is believed to contributepredominantly to the conversion of feed to the gasoline products.Heretofore, the zeolite-containing hydrocracking catalysts of the priorart have required that certain penalties be endured for the optimizationof particular process variables or product characteristics, e.g., octanenumber.

The non-zeolitic molecular sieves employed in the instant invention areselected from the hereinafter described group of non-zeolitic molecularsieves as being characterized in their calcined form by an adsorption ofoxygen of at least 4 percent by weight at a partial pressure of 100 torrand a temperature of -186° C., and further by an adsorption of isobutaneof at least 2 percent by weight at a partial pressure of 500 torr and atemperature of 20° C. The non-zeolitic molecular sieves employed in theinstant invention are most preferably characterized by theaforementioned adsorption criteria and also characterized by anadsorption of triethylamine from zero to less than 5 percent by weight,preferably less than 3 percent by weight, at a partial pressure of 2.6torr and a temperature of 22° C. The preferred non-zeolitic molecularsieves thus have either large or medium pore sizes, the latter beingmost preferred.

NON-ZEOLITIC MOLECULAR SIEVES

The term "non-zeolitic molecular sieves" are "NZMS" is defined in theinstant invention to include the "SAPO" molecular sieves of U.S. Pat.No. 4,440,871, "ELAPSO" molecular sieves as disclosed in U.S. Ser. No.600,312, filed Apr. 13, 1984 continued as U.S. Ser. No. 764,618, filedAug. 12, 1988, now U.S. Pat. No. 4,735,928, and certain "MeAPO","FeAPO", "TAPO" and "ELAPO" molecular sieves, as hereinafter described.Crystalline metal aluminophosphates (MeAPOs where "Me" is at least oneof Mg, Mn, Co and Zn) are disclosed in U.S. Pat. No. 4,567,029, issuedJan. 28, 1986; crystalline ferroaluminophosphates (FeAPOs) are disclosedin U.S. Pat. No. 4,554,143, issued Nov. 19, 1985; titaniumaluminophosphates (TAPOs) are disclosed in U.S. Pat. No. 4,500,651,issued Feb. 19, 1985; certain non-zeolitic molecular sieves ("ELAPO")are disclosed in EPC Patent Application 85104386.9 (Publication No.0158976, published Oct. 13, 1985) and 85104388.5 (Publication No.158349, published Oct. 16, 1985); and ELAPSO molecular sieves aredisclosed in copending U.S. Ser. No. 600,312 filed Apr. 13, 1984 nowU.S. Pat. No. 4,735,928 (EPC Publication No. 0159624, published Oct. 30,1985). The aforementioned applications and patents are incorporatedherein by reference thereto. The nomenclature employed herein to referto the members of the aforementioned NZMSs is consistent with thatemployed in the aforementioned applications or patents. A particularmember of a class is generally referred to as a "-n" species wherein "n"is an integer, e.g., SAPO-11, MeAPO-11 and ELAPSO-31. In the followingdiscussion on NZMSs set forth hereinafter the mole fraction of the NZMSsare defined as compositional values which are plotted in phase diagramsin each of the identified patents, published applications or copendingapplications.

ELAPSO MOLECULAR SIEVES

"ELAPSO" molecular sieves are described in copending U.S. Ser. No.600,312, filed Apr. 13, 1984, (EPC Publication No. 0159,624, publishedOct. 30, 1985, incorporated herein by reference) as crystallinemolecular sieves having three-dimensional microporous frameworkstructures of ELO₂, ALO₂, PO₂, SiO₂ oxide units and having an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has avalue offrom zero to about 0.3; "EL" represents at least one element capable offorming a three dimensional oxide framework, "EL" being characterized asan element having a mean "T-O" distance in tetrahedral oxide structuresbetween about 1.51 Angstroms and about 2.06 Angstroms, "EL" having acation electonegativity between about 125 kcal/g-atom to about 310kcal/gm-atom and "EL" being capable of forming stable M-O-P, M-O-Al orM-O-M bonds in crystalline three dimensional oxide structures having a"M-O" bond dissociation energy greater than about 59 kcal/g-atom at 298°K.; and "w", "x", "y" and "z" represent the mole fractions of "EL",aluminum, pyhosphorus and silicon, respectively, present as frameworkoxides, said mole fractions being within the limiting compositionalvalues or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x             y           (z + w)                                      ______________________________________                                        A      0.60          0.39 - (0.01)p                                                                            0.01(p + 1)                                  B      0.39 - (0.01 p)                                                                             0.60        0.01(p + 1)                                  C      0.01          0.60        0.39                                         D      0.01          0.01        0.98                                         E      0.60          0.01        0.39                                         ______________________________________                                    

where "p" is an integer corresponding to the number of elements "El" inthe (El_(w) Al_(x) P_(y) Si_(z))O₂ constituent. The "ELAPSO" molecularsieves are also described as crystalline molecular sieves havingthree-dimensional microporous framework structures of ELO₂, AlO₂, SiO₂and PO₂ tetrahedral oxide units and having an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; "EL" represents at least one element capable offorming a framework tetrahedral oxide and is selected from the groupconsisting of arsenic, beryllium, boron, chromium, cobalt, gallium,germanium, iron, lithium, magnesium, manganese, titanium and zinc; and"w", "x", "y" and "z" repesent the mole fractions of "EL", aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides,said mole fractions being within the limiting compositional values orpoints as follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x             y           (z + w)                                      ______________________________________                                        a      0.60          0.39 - (0.01)p                                                                            0.01(p + 1)                                  b      0.39 - (0.01 p)                                                                             0.60        0.01(p + 1)                                  c      0.10          0.55        0.35                                         d      0.55          0.10        0.35                                         ______________________________________                                    

where "p" is as above defined.

The "ELAPSO" molecular sieves include numerous species which areintended herein to be within the scope of the term "non-zeoliticmolecular sieves" such being disclosed in the following copending andcommonly assigned applications, incorporated herein by reference thereto[(A) following a serial number indicates that the application isabandoned, while (CIP) following a serial number indicates that theapplication is a continuation-in-part of the immediately precedingapplication and (C) indicates that the application is a continuation ofthe immediately preceding application]:

    ______________________________________                                        U.S. Ser. No.                                                                              Filed         NZMS                                               ______________________________________                                        599,808(A)   April 13, 1984                                                                              AsAPSO                                             845,484(CIP) March 31, 1986                                                                              AsAPSO                                             600,177(A)   April 13, 1984                                                                              BAPSO                                              845,255(CIP) March 28, 1986                                                                              BAPSO                                              600,176(A)   April 13, 1984                                                                              BeAPSO                                             841,752(CIP) March 20, 1986                                                                              BeAPSO                                             599,830(A)   April 13, 1984                                                                              CAPSO                                              852,174(CIP) April 15, 1986                                                                              CAPSO                                              599,925(A)   April 13, 1984                                                                              GaAPSO                                             845,985(CIP) March 31, 1986                                                                              GaAPSO                                             599,971(A)   April 13, 1984                                                                              GeAPSO                                             852,175(CIP) April 15, 1986                                                                              GeAPSO                                             599,952(A)   April 13, 1984                                                                              LiAPSO                                             847,227(CIP) April 2, 1986 LiAPSO                                             600,179      April 13, 1984                                                                              TiAPSO                                             (now U.S. Pat. No. 4,684,617 issued August 4, 1987)                           049,274 (C)  May 13, 1987  TiAPSO                                             600,180      April 13, 1984                                                                              MgAPSO                                             600,175      April 13, 1984                                                                              MnAPSO                                             (now U.S. Pat. No. 4,686,092 issued August 11, 1987)                          600,174      April 13, 1984                                                                              CoAPSO                                             600,170      April 13, 1984                                                                              ZnAPSO                                             600,173      April 13, 1984                                                                              FeAPSO                                             (now U.S. Pat. No. 4,683,217 issued July 28, 1987)                            600,168(A)   April 13, 1984                                                                              QuinAPSO                                           63,791(C)    June 23, 1987 QuinAPSO                                           600,181      April 13, 1984                                                                              QuinAPSO                                           600,182      April 13, 1984                                                                              CoMnMgAPSO                                         57,648(C)    June 9, 1987  CoMnMgAPSO                                         600,183      April 13, 1984                                                                              SenAPSO                                            ______________________________________                                    

TiAPSO MOLECULAR SIEVES

The TiAPSO molecular sieves of U.S. Ser. No. 600,179, filed Apr. 13,1984 (now U.S. Pat. No. 4,684,617) have three-dimensional microporousframework structures of TiO₂, AlO₂, PO₂ and SiO₂ tetrahedral oxide unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Ti.sub.w Al.sub.x P.sub.y Si.sub.z)o.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ti_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of titanium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each has a value of at least 0.01. Themole fractions "w", "x", "y" and "z" are generally defined as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a subclass of TiAPSO molecular sieves the values "w", "x", "y" and"z" in the above formula are within the tetragonal compositional areadefined by points a, b, c and d, said points a, b, c and d representingthe following values for "w", "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

TiAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing active sources oftitanium, silicon, aluminum and phosphorus, and preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C. until crystals of the TiAPSO product areobtained, usually a period of from hours to several weeks. Generally,the crystallization time is from about 2 hours to about 30 days andtypically from about 4 hours to about 20 days. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the TiAPSO, it is preferred to employ a reaction mixturecomposition expressed in terms of the molar ratios as follows:

    aR:(Ti.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y" and "z" represent themole fractions of titanium, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing titanium,aluminum, phosphorus and silicon as framework tetrahedral oxides areprepared as follows:

PREPARATIVE REAGENTS

TiAPSO compositions are typically prepared using numerous reagents.Typical reagents which may be employed and abbreviations employed inU.S. Ser. No. 600,179 for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) Tiipro: titanium isopropoxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ NH: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH); and

(j) C-hex: cyclohexylamine.

PREPARATIVE PROCEDURES

TiAPSOs may be prepared by forming a starting reaction mixture by addingthe H₃ PO₄ and the water. This mixture is mixed and to this mixturealuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture the LUDOX-LS is addedand the resulting mixture blended (about 2 minutes) until a homogeneousmixture is observed.

The titanium isopropoxide is added to the above mixture and theresulting mixture blended until a homogeneous mixture is observed. Theorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. When the organic templating agent is quinuclidinethe procedure is modified such that the quinuclidine is dissolved inabout one half the water and accordingly the H₃ PO₄ is mixed with aboutone half the water. (The pH of the mixture is measured and adjusted fortemperature). The mixture is then placed in a lined(polytetrafluoroethylene) lined stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C.) for a time or placed inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

The products are removed from the reaction vessel and cooled.

MgAPSO MOLECULAR SIEVES

The MgAPSO molecular sieves of U.S. Ser. No. 600,180, filed Apr. 13,1984 have three-dimensional microporous framework structures of MgO₂ ⁻,AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Mg_(w) Al_(x) P_(y) Si_(z))O₂ and has a value fromzero (0) to about 0.3; and "w", "x", "y" and "z" represent the molefractions of magnesium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each preferably has a value of atleast 0.01. The mole fractions "w", "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.39         0.59   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the MgAPSO molecular sieves the values "w","x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

MgAPSO compositions are generally synthesized by hydrothermalcrystallization for an effective time at effective pressures andtemperatures from a reaction mixture containing reactive sources ofmagnesium, silicon, aluminum and phosphorus, an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C. until crystals of the MgAPSO product are obtained,usually a period of from several hours to several weeks. Generally, thecrystallization period will be from about 2 hours to about 30 days withit typically being from about 4 hours to about 20 days for obtainingMgAPSO crystals. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the MgAPSO compositions, it is preferred to employreaction mixture compositions expressed in terms of the molar ratios asfollows:

    aR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and can have a value within the range of from zero(0) to about 6 and is more preferably an effective amount greater thanzero to about 6; "b" has a value of from zero (0) to about 500,preferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing magnesium,aluminum, phosphorus and silicon as framework tetrahedral oxides areprepared as follows:

PREPARATIVE REAGENTS

MgAPSO compositions are prepared using numerous reagents. Typicalreagents which may be employed to prepare MgAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea for hydrated pseudoboehmite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Mg(Ac)₂ : magnesium acetate tetrahydrate, Mg(C₂ H₃ O₂).4H₂ O;

(e) H₃ PO₄ : 85 weight percent aqueous phosphoric acid in water;

(f) TBAOH: tetrabutylammonium hydroxide (40 wt.% in water);

(g) Pr₂ NH: di-n-propylamine;

(h) Pr₃ NH: tri-n-propylamine;

(i) Quin: Quinuclidine;

(j) MQuin: Methyl Quinuclidine hydroxide, (17.9% in water);

(k) C-hex: cyclohexylamine;

(l) TEAOH: tetraethylammonium hydroxide (40 wt.% in water);

DEEA: Diethylethanolamine;

(n) i-Pr₂ NH: di-isopropylamine;

(o) TEABr: tetraethylammonium bromide; and

(p) TPAOH: tetrapropylammonium hydroxide (40 wt.% in water).

PREPARATIVE PROCEDURES

The MgAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, magnesium(expressed as the oxide), SiO₂, Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂O₅) and H₂ O, respectively.

The reaction mixtures may be prepared by the following representativeprocedures, designated hereinafter as Methods A, B and C.

METHOD A

The reaction mixture is prepared by mixing the ground aluminum source(Alipro or CATAPAL) with the H₃ PO₄ and water on a gradual basis withoccasional cooling with an ice bath. The resulting mixture is blendeduntil a homogeneous mixture is observed. When the aluminum source isCATAPAL the water and H₃ PO₄ are first mixed with the CATAPAL addedthereto. The magnesium acetate is dissolved in a portion of the waterand is then added followed by addition of the LUDOX-LS. The combinedmixture is blended until a homogeneous mixture is observed. The organictemplating agent is added to this mixture and blended until ahomogeneous mixture is observed. The resulting mixture (final reactionmixture) is placed in a lined (polytetrafluoro-ethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) foran effective time. Alternatively, if the digestion temperature is 100°C. the final reaction mixture is placed in a lined(polytetrafluoroethylene) screw top bottle for a time. Digestions aretypically carried out under autogenous pressure. The products areremoved from the reaction vessel, cooled and evaluated as set forthhereinafter.

METHOD B

When method B is employed the organic templating agent isdi-n-propylamine. The aluminum source, silicon source and one-half ofthe water are first mixed and blended until a homogeneous mixture isobserved. A second solution was prepared by mixing the remaining water,the H₃ PO₄ and the magnesium acetate. This solution is then added to theabove mixture. The magnesium acetate and H₃ PO₄ solution is then addedto the above mixture and blended until a homogeneous mixture isobserved. The organic templating agent(s) is/are then added and theresulting reaction mixture digested and product recovered as in MethodA.

METHOD C

Method C is carried out by mixing aluminum isopropoxide, LUDOX LS andwater in a blender or by mixing water and aluminum iso-propoxide in ablender followed by addition of the LUDOX LS. H₃ PO₄ and magnesiumacetate are then added to this mixture. The organic templating agent isthen added to the resulting mixture and digested and product recoveredas in Method A.

MnAPSO MOLECULAR SIEVES

The MnAPSO molecular sieves of U.S. Ser. No. 600,175, filed Apr. 13,1984 (now U.S. Pat. No. 4,686,092 issued Aug. 11, 1987), have aframework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of the elements manganese, aluminum, phosphorus and silicon,respectively, present as tetrahedral oxides. The mole fractions "w","x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

The values of w, x, y and z may be as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

MnAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofmanganese, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theMnAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the MnAPSo compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y" and "z" represent themole fractions of manganese, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing manganese,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

PREPARATIVE REAGENTS

MnAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare MnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

MnAPSOs are prepared by forming a starting reaction mixture by addingthe H₃ PO₄ to one half of the quantity of water. This mixture is mixedand to this mixture the aluminum isopropoxide or CATAPAL is added. Thismixture is then blended until a homogeneous mixture is observed. To thismixture the LUDOX LS is added and the resulting mixture blended (about 2minutes) until a homogeneous mixture is observed. A second mixture isprepared using the manganese acetate and the remainder (about 50%) ofthe water. The two mixtures are admixed and the resulting mixtureblended until a homogeneous mixture is observed. The organic templatingagent is then added to the resulting mixture and the resulting mixtureblended until a homogeneous mixture is observed, i.e., about 2 to 4minutes. (The pH of the mixture is measured and adjusted fortemperature). The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out at the autogenous pressure.

CoAPSO MOLECULAR SIEVES

The CoAPSo molecular sieves of U.S. Ser. No. 600,174, filed Apr. 13,1984 have three-dimensional microporous framework structures of CoO₂ ⁻,AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, where the mole fractions "w", "x", "y"and "z" are each at least 0.01 and are generally defined, as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CoAPSO molecular sieves the values of"w", "x", "y", and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

CoAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, silicon, aluminum and phosphorus, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is generally placed in a sealed pressure vessel, preferablylined with an inert plastic material such as polytetrafluoroethylene andheated, preferably under autogenous pressure at an effective temperaturewhich is generally between 50° C. and 250° C. and preferably between100° C. and 200° C. until crystals of the CoAPSO product are obtained,usually for an effective time of from several hours to several weeks.Generally the effective crystallization time will be from about 2 hoursto about 30 days and typically from about 4 hours to about 20 days. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the CoAPSO, it is preferred to employ a reaction mixturecomposition expressed in terms of the molar ratios as follows:

    aR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively, andeach has a value of at least 0.01. In a preferred embodiment thereaction mixture is selected such that the mole fractions "w", "x", "y"and "z" are generally defined as being within the limiting compositionalvalues or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing cobalt, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

CoAPSO compositions may be prepared using numerous reagents. Reagentswhich may be employed to prepared CoAPSOs include:

(a) Alipro: aluminum isopropoxide; p0 (b) CATAPAL: Trademark of CondeaCorporation for pseudoboehmite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Co(Ac)₂ : cobalt acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(e) CoSO₄ : cobalt sulfate, (CoSO₄.7H₂ O);

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TBAOH: tetrabutylammonium hydroxide (25 wt% in methanol);

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TEAOH: tetraethylammonium hydroxide (40 wt. % in water);

(n) DEEA: diethanolamine;

(o) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water); and

(p) TMAOH: tetrametylammonium hydroxide (40 wt. % in water).

PREPARATIVE PROCEDURE

CoAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fCoO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, h, i, g and j represent the moles of template R, cobalt(expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are prepared by forming a starting reactionmixture comprising the H₃ PO₄ and one half of the water. This mixture isstirred and the aluminum source (Alipro or CATAPAL) added. The resultingmixture is blended until a homogeneous mixture is observed. The LUDOX-LSis then added to the reslting mixture and the new mixture blended untila homogeneous mixture is observed. The cobalt source (e.g., Co(Ac)₂,Co(SO₄) or mixtures thereof) is dissolved in the remaining water andcombined with the first mixture. The combined mixture is blended until ahomogeneous mixture is observed. The organic templating agent is addedto this mixture and blended for about two to four minutes until ahomogeneous mixture is observed. The resulting mixture (final reactionmixture) is placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C., 200° C. or 225°C.) for a time. Digestions are typically carried out at the autogenouspressure. The products are removed from the reaction vessel and cooled.

ZnAPSO MOLECULAR SIEVES

The ZnAPSO molecular sieves of U.S. Ser. No. 600,170, filed Apr. 13,1984 comprise framework structures of ZnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Zn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of zinc, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each has a value of at least 0.01. Themole fractions "w", "x", "y" and "z" are generally defined being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of ZnAPSO molecular sieves the values "w", "x","y" and "z" in the above formula are within the limiting compositionalvalues or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

ZnAPSO compositions are generally synthesized by hydrothermalcrystallization at effective process conditions from a reaction mixturecontaining active sources of zinc, silicon, aluminum and phosphorus,preferably an organic templating, i.e., structure-directing, agent,preferably a compound of an element or Group VA of the Periodic Table,and/or optionally an alkali of other metal. The reaction mixture isgenerally placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure, at a temperature between 50° C.and 250° C., and preferably between 100° C. and 200° C. until crystalsof the ZnAPSO product are obtained, usually a period of from severalhours to several weeks. Generally the effective crystallization periodis from about 2 hours to about 30 days with typical periods of fromabout 4 hours to about 20 days being employed to obtain ZnAPSO products.The product is recovered by any convenient method such as centrifugationor filtration.

In synthesizing the ZnAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, morepreferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of zinc, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01. In a preferredembodiment the reaction mixture is selected such that the mole fractions"w", "x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 moles. Molecular sieves containing zinc, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

ZnAPSO compositions are typically prepared using numerous reagents.Reagents which may be employed to prepare ZnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) ZnAc: Zinc Acetate, Zn(C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH₃)₄ NOH.5H₂ O;

(i) TPAOH: 40 weight percent aqueous solution of tetrapropylammoniumhydroxide, (C₃ H₇)₄ NOH;

(j) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(k) Pr₃ N: Tri-n-propylamine, (C₃ H₇)₃ N;

(l) Quin: Quinuclidine, (C₇ H₁₃ N);

(m) C-hex: cyclohexylamine; and

(n) DEEA: diethylethanolamine, (C₂ H₅)₂ NC₂ H₅ OH.

PREPARATIVE PROCEDURE

ZnAPSO compositions are typically prepared by forming reaction mixtureshaving a molar composition expressed as:

    eR:fZnO:gAl.sub.2 O.sub.3 :hP.sub.2 O.sub.5 :iSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, zinc(expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are generally prepared by forming a startingreaction mixture comprising the H₃ PO₄ and a portion of the water. Thismixture is stirred and the aluminum source added. The resulting mixtureis blended until a homogeneous mixture is observed. The LUDOX LS is thenadded to the resulting mixture and the new mixture blended until ahomogeneous mixture is observed. The zinc source (zinc acetate) isdissolved in the remaining water and combined with the first mixture.The combined mixture is blended until a homogeneous mixture is observed.The organic templating agent is added to this mixture and blended forabout two to four minutes until a homogeneous mixture is observed. Theresulting mixture (final reaction mixture) is placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat an effective temperature for an effective time. Digestions aretypically carried out under autogenous pressure. The products areremoved from the reaction vessel and cooled.

FeAPSO MOLECULAR SIEVES

The FeAPSO molecular sieves of U.S. Ser. No. 600,173, filed Apr. 13,1984 (now U.S. Pat. No. 4,683,217) have three-dimensional microporouscrystal framework structures of FeO₂ ⁻², (and/or FeO₂ ⁻), AlO₂ ⁻, PO₂ ⁺and SiO₂ tetrahedral oxide units and having a unit empirical formula, onan anhydrous basis, of:

    mR:(Fe.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero (0) to about 0.3; the maximum value of "m" in each casedepends upon the molecular dimensions of the templating agent and theavailable void volume of the pore system of the particular molecularsieve involved; and "w", "x", "y" and "z" represent the mole fractionsof iron, aluminum, phosphorus and silicon, respectively, present astetrahedral oxides, said mole fractions being such that they are withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

The values of w, x, y and z may be as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

The FeAPSOs of the instant invention are generally synthesized byhydrothermal crystallization from a reaction mixture comprising reactivesources of iron, aluminum, phosphorus and silicon, and preferably one ormore organic templating agents. Optionally, alkali or other metal(s) maybe present in the reaction mixture and may act as templating agents. Thereaction mixture is generally placed in a pressure vessel, preferablylined with an inert plastic material, such as polytetrafluoroethylene,and heated, preferably under autogenous pressure, at an effectivetemperature which is generally between about 50° C. and about 250° C.,and preferably between about 100° C. and 200° C., until crystals of theFeAPSO product are obtained, usually a period of from several hours toseveral weeks. Molecular sieves containing iron, aluminum, phosphorusand silicon as framework tetrahedral oxide units are typically preparedas follows:

PREPARATIVE REAGENTS

FeAPSO compositions may be prepared using numerous reagents. Reagentswhich may employed to prepare FeAPSOs include:

(a) Alipro: aluminum isopropoxide, Al(OCH(CH₃)₂)₃ ;

(b) LUDOX-LS: LUDOX-LS is the trademark of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: trademark for hydrated aluminum oxide containing about 75wt. percent Al₂ O₃ (pseudoboehmite phase) and about 25 wt. percentwater;

(d) Fe(Ac)₂ : Iron (II) acetate;

(e) FeSO₄ : Iron (II) sulfate hexahydrate;

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; p0 (h) TBAOH: 40 weight percent aqueous solution oftetrabutylammonium hydroxide;

(i) Pr₂ NH: di-n-propylamine ((C₃ H₇)₂ NH);

(j) Pr₃ N: tri-n-propylamine ((C₃ H₇)₃ N);

(k) Quin: Quinuclidine (C₇ H₁₃ N);

(l) MQuin: Methyl Quinuclidine hydroxide (C₇ H₁₃ NCH₃ OH);

(m) TMAOH: tetramethylammonium hydroxide pentahydrate; and

(o) C-hex: cyclohexylamine.

PREPARATIVE PROCEDURES

(a) Reaction mixtures to prepare FeAPSOs are typically prepared bygrinding an aluminum isopropoxide in a blender followed by slowly addinga H₃ PO₄ solution with mixing. A solution/dispersion of iron acetate inwater is added and then a silica (e.g., LUDOX-LS) is added. The organictemplating agent is then added to this mixture, or in some casesone-half of this mixture, and the mixture blended to form a homogeneousmixture. For example, in one embodiment, the number of moles of eachcomponent in the reaction mixture is as follows:

    ______________________________________                                               Component                                                                             Moles                                                          ______________________________________                                               Al.sub.2 O.sub.3                                                                      0.9                                                                   P.sub.2 O.sub.5                                                                       0.9                                                                   SiO.sub.2                                                                             0.2                                                                   FeO*    0.2                                                                   TEAOH   1.0                                                                   H.sub.2 O                                                                             50                                                             ______________________________________                                    

The reaction mixture is sealed in a stainless steel pressure vessellined with polytetrafluoroethylene and heated in an oven at atemperature, time and under autogenous pressure. The solid reactionproduct is recovered by filtration, washed with water and dried at roomtemperature.

(b) In another embodiemtn, reaction mixtures are prepared by grindingthe aluminum isopropoxide in a blender followed by addition of asolution/dispersion of iron (II) acetate. H₃ PO₄ is added to thismixture and the resulting mixture blended to form a homogeneous mixture.A silica (e.g., LUDOX-LS) is added to this mixture except that in someinstances the silica may be added with the H₃ PO₄. The resultingmixtures were blended until a homogeneous mixture is observed. Organictemplating agent is added to each mixture and the resulting mixturesplaced in a stainless steel pressure vessel lined withpolytetrafluoroethylene and heated, washed and the product recovered. Inthis embodiment the number of moles of each component in the reactionmixture is as follows:

    ______________________________________                                               Component                                                                             Moles                                                          ______________________________________                                               Al.sub.2 O.sub.3                                                                      0.9                                                                   P.sub.2 O.sub.5                                                                       0.9                                                                   SiO.sub.2                                                                             0.2                                                                   FeO*    0.2                                                                   Template                                                                              1.0                                                                   H.sub.2 O                                                                             50                                                             ______________________________________                                         *Iron(II) acetate reported as Iron(II) oxide.                            

QUINARY MOLECULAR SIEVES

The QuinAPSO quinary molecular sieves of U.S. Ser. Nos. 600,168 and600,181, both filed Apr. 13, 1984, have three-dimensional microporousframework structures of MO₂, AlO₂, PO₂ and SiO₂ tetrahedral units havingan empirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(w) P_(y) Si_(z))O₂ and has a value offrom zero (0) to about 0.3; M represents at least two elements selectedfrom the group consisting of arsenic, beryllium, boron, chromium,cobalt, gallium, germanium, iron, lithium, magnesium, manganese,titanium, vanadium and zinc; and "w", "x", "y" and "z" represent themole fractions of M, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides. Preferably, M represents the combinationof cobalt and manganese. The mole fractions "w", "x", "y", and "z" aregenerally defined as being within the limiting compositional values orpoints as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.37   0.03                                             B       0.37          0.60   0.03                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

Preferably the mole fractions w, x, y and z will fall within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.60          0.37   0.03                                             b       0.37          0.60   0.03                                             c       0.01          0.60   0.39                                             d       0.01          0.39   0.60                                             e       0.39          0.01   0.60                                             f       0.60          0.01   0.39                                             ______________________________________                                    

QuinAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe elements M, aluminum, phosphorus and silicon and preferably anorganic templating agent, i.e., structure-directing agent. Thestructure-directing agents are preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureand at typical effective temperatures between 50° C. and 250° C.,preferably between 100° C. and 200° C., until crystals of the QuinAPSOproduct are obtained, usually over a period of from several hours toseveral weeks. Typical effective crystallization times are from about 2hours to 30 days with from about 4 hours to about 20 days beinggenerally employed to obtain QuinAPSO products. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the QuinAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y", and "z" represent themole fractions of elements M, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.37   0.03                                             G       0.37          0.60   0.03                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. QuinAPSO compositions were prepared usingnumerous regents; the appropriate sources of the various elements M arethe same as those used in the preparation of the various APO and APSOmolecular sieves containing the same elements, as described in detailabove and below.

Reagents which may be employed to prepare QuinAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent phosphoric acid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O (for QuinAPSOscontaining manganese);

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O (for QuinAPSOs containingcobalt);

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

PREPARATIVE PROCEDURES

QuinAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture a silica (e.g.,LUDOX-LS) is added and the resulting mixture blended (about 2 minutes)until a homogeneous mixture is observed. A second mixture is preparedusing manganese acetate (or a appropriate source of another element M)and one half of the remaining water. A third mixture is prepared usingcobalt acetate (or a appropriate source of another element M) and onehalf of the remaining water. The three mixtures are admixed and theresulting mixture blended until a homogeneous mixture is observed. Theorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. The pH of the mixture is measured and adjusted fortemperature. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat an effective temperature for an effective time. Digestions aretypically carried out under autogenous pressure.

CoMnMgAPO MOLECULAR SIEVES

The CoMnMgAPSO senary molecular sieves of U.S. Ser. No. 600,182, filedApr. 13, 1984, and of U.S. Ser. No. 057,648 filed June 9, 1987, havethree-dimensional microporous framework structures of CoO₂ ⁻², MnO₂ ⁻²,AlO₂, PO₂ and SiO₂ tetrahedral oxide units having an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ and hasa value of from zero (0) to about 0.3; "t", "u", and "v", "x", "y" and"z" represent the mole fractions of cobalt, manganese, magnesium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides and each has a value of at least 0.01. The mole fractions "t","u", "v", "x", "y" and "z" are generally defined as being within thelimiting composition values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.36   0.04                                            B        0.36          0.60   0.04                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the CoMnMgAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.55          0.41   0.04                                            b        0.41          0.55   0.04                                            c        0.10          0.55   0.35                                            d        0.55          0.10   0.35                                            ______________________________________                                    

CoMnMgAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, manganese, magnesium, aluminum, phosphorus and silicon, andpreferably an organic templating agent, i.e., structure-directing,agent. The structure-directing agents are preferably a compound of anelement of Group VA of the Periodic Table, and/or optionally an alkalior other metal. The reaction mixture is generally placed in a sealedpressure vessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C., until crystals of the CoMnMgAPSO product are obtained,usually over a period of from several hours to several weeks. Typicalcrystallization times are from about 2 hours to about 30 days with fromabout 4 hours to about 20 days generally being employed to obtainCoMnMgAPSO products. The product is recovered by any convenient methodsuch as centrifugation or filtration.

In synthesizing the CoMnMgAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6 and more preferably from greater than zero to about 2; "b"has a value of from zero (0) to about 500, preferably between about 2and about 300; and "t", "u", "v", "x", "y", and "z" represent the molefractions of cobalt, manganese, magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that themole fractions "w", "x", "y" and "z", where "w" is the sum of"t"+"u"+"v", are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.36   0.04                                            G        0.36          0.60   0.04                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "t", "u", "v", "x", "y" and"z" such that (t+u+v+x+y+z)=1.00 mole. Molecular sieves containingcobalt, manganese, magnesium, aluminum, phosphorus and silicon asframework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

CoMnMgAPSO compositions may be prepared by using numerous reagents.Reagents which may be employed to prepare CoMnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of Du Pont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : aqueous solution which is 85 weight percent phosphoricacid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(f) MgAc: Magnesium Acetate Mg(C₂ H₃ O₂).4H₂ O;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

PREPARATIVE PROCEDURES

CoMnMgAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. This mixture a silica (e.g., LUDOX-LS)is added and the resulting mixture blended (about 2 minutes) until ahomogeneous mixture is observed.

Three additional mixtures are prepared using cobalt acetate, magnesiumacetate and manganese acetate using one third of the remainder of thewater for each mixture. The four mixtures are then admixed and theresulting mixture blended until a homogeneous mixture is observed. Anorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature for a time. Digestions are typically carried out underautogenous pressure.

SenAPSO MOLECULAR SIEVES

The SenAPSO molecular sieves of U.S. Ser. No. 600,183, filed Apr. 13,1984 have three-dimensional microporous framework structures of MO₂^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units, where "n" is -3,-2, -1, 0 or +1, and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(w) Al_(x) P_(y) Si_(z))O₂, and has a value offrom zero to about 0.3; "M" represents three elements selected from thegroup consisting of arsenic, beryllium, boron, chromium, cobalt,gallium, germanium, iron, lithium, magnesium, manganese, titanium,vanadium and zinc; "n" may have the aforementioned values depending uponthe oxidation state of "M"; and "w", "x", "y" and "z" represent the molefractions of elements "M", aluminum, phosphorus and silicon,respectively, present as tetrahedral oxides. The mole fractions "w","x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows, wherein "w" denotes thecombined mole fractions of the three elements "M" such that "w"="w₁"+"w₂ "+"w₃ " and each element "M" has a mole fraction of at least 0.01:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.36   0.04                                            B        0.36          0.60   0.04                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the SenAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.36   0.04                                            b        0.36          0.60   0.04                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

SenAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofelements "M", aluminum, phosphorus and silicon, and preferably anorganic templating, i.e., structure-directing, agent. Thestructure-directing agents are preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C., until crystals of the SenAPSO product are obtained,usually over a period of from several hours to several weeks. Typicalcrystallization times are from about 2 hours to about 30 days with fromabout 4 hours to about 20 days generally being employed to obtainSenAPSO products. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the SenAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6 and more preferably from greater than zero to about 2; "b"has a value of from zero (0) to about 500, preferably between about 2and about 300; and "w", "x", "y", and "z" represent the mole fractionsof elements "M", aluminum, phosphorus and silicon, respectively, andeach has a value of at least 0.01, with the proviso that each "M" ispresent in a mole fraction of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that themole fractions "w", "x", "y" and "z" are generally defined as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.36   0.04                                            G        0.36          0.60   0.04                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. The SenAPSO molecular sieves are prepared bypreparative techniques, and using sources of the elements "M" similar tothose described for the other APSO molecular sieves described above andbelow.

AsAPSO MOLECULAR SIEVES

The AsAPSO molecular sieves of U.S. Ser. No. 599,808, filed Apr. 13,1984, and U.S. Ser. No. 845,484 filed Mar. 31, 1986 have a frameworkstructure of AsO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units havingan empirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(As.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 ps

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (As_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements arsenic,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the AsAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the AsAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        g        0.50          0.40   0.10                                            h        0.42          0.48   0.10                                            i        0.38          0.48   0.14                                            j        0.38          0.37   0.25                                            k        0.45          0.30   0.25                                            l        0.50          0.30   0.20                                            ______________________________________                                    

AsAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofarsenic, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theAsAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 10 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the AsAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(As.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 60; and "w", "x", "y" and "z"represent the mole fractions of arsenic, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from about 1to about 2 total moles of silicon and arsenic, and from about 1 to about2 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing arsenic, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

AsAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare AsAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) As₂ O₅, arsenic(V) oxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclinidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

AsAPSOs may be prepared by forming a starting reaction mixture bydissolving the arsenic(V) oxide and the H₃ PO₄ in at least part of thewater. To this solution the aluminum isopropoxide or CATAPAL is added.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent and then the silica is added and theresulting mixture blended until a homogeneous mixture is observed. Themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

BAPSO MOLECULAR SIEVES

The BAPSO molecular sieves of U.S. Ser. No. 600,177, filed Apr. 13,1984, and U.S. Ser. No. 845,255 filed Mar. 28, 1986 have a frameworkstructure of BO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(B.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (B_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements boron,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the BAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the BAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        g        0.51          0.42   0.07                                            h        0.45          0.48   0.07                                            i        0.33          0.48   0.19                                            j        0.33          0.38   0.29                                            k        0.36          0.35   0.29                                            l        0.51          0.35   0.14                                            ______________________________________                                    

BAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofboron, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theBAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the BAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(B.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from (0) to about 500, preferably between about 2 and about 300, mostpreferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of boron, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about1.0 to about 2 total moles of silicon and boron, and from about 0.75 toabout 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing boron, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

BASPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) H₃ BO₃, boric acid, and trialkyl borates;

(f) TEAOH: 40 weightpercent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

BAPSOs may be prepared by forming a starting reaction mixture bydissolving aluminum isopropoxide in an alcohol such as isopropanol,adding the H₃ PO₄ and recovering the solid which precipitates. Thissolid is then added to water, and trialkylborate (for example trimethylborate added, followed by silica and the templating agent. This mixtureis then blended until a homogeneous mixture is observed. The mixture isthen placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) for atime or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

BeAPSO MOLECULAR SIEVES

The BeAPSO molecular sieves of U.S. Ser. No. 600,176, filed Apr. 13,1984, and U.S. Ser. No. 841,752 filed Mar. 20, 1986 have a frameworkstructure of BeO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempircal chemical composition on an anhydrous basis expressed by theformula:

    mR:(Be.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore systems; "m" represents the molar amount of"R" present per mole of (Be_(x) Al_(x) P_(y) Si_(z))O₂ and has a valueof zero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements beryllium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the BeAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.60          0.38   0.02                                             b       0.38          0.60   0.02                                             c       0.01          0.60   0.39                                             d       0.01          0.39   0.60                                             e       0.39          0.01   0.60                                             f       0.60          0.01   0.39                                             ______________________________________                                    

BeAPSO compositions are generaly synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofberyllium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe BeAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, have been observed,with from 1 to 10 days being preferred. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the BeAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Be.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most peferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of beryllium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing beryllium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

PREPARATIVE REAGENTS

BeAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BeAPSOs include:

(a) Alipro: alumimun isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) beryllium sulfate, BeSO₄ ;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

BeAPSOs may be prepared by forming a starting solution by mixing H₃ PO₄in at least part of the water. To this solution is added berylliumsulfate (or another beryllium salt) and the resultant mixture stirreduntil a homogeneous solution is obtained. To this solution may be addedsuccessively the aluminum oxide, the silica and the templating agent,with the mixture being stirred between each addition until it ishomogeneous. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

CAPSO MOLECULAR SIEVES

The CAPSO molecular sieves of U.S. Ser. No. 599,830, filed Apr. 13,1984, and U.S. Ser. No. 852,174 filed Apr. 15, 1986 have a frameworkstructure of CrO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units (where"n" is -1, 0 or +1) having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Cr_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements chromium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.60          0.38   0.02                                             b       0.38          0.60   0.02                                             c       0.01          0.60   0.39                                             d       0.01          0.39   0.60                                             e       0.39          0.01   0.60                                             f       0.60          0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the CAPSO molecular sieves, thevalues of x and y in the above formula are each within the range ofabout 0.4 to 0.5 and (z+w) is in the range of about 0.02 to 0.15.

Since the exact nature of the CAPSO molecular sieves is not clearlyunderstood at present, although all are believed to contain CrO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the CAPSO molecular sievesby means of their chemical composition. This is due to the low level ofchromium present in certain of the CAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between chromium, aluminum, phosphorus and silicon. As aresult, although it is believed that CrO₂ tetrahedra are substitutedisomorphously for AlO₂, PO₂ or SiO₂ tetrahedra, it is appropriate tocharacterize certain CAPSO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

CAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofchromium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe CAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, and preferablyabout 1 to about 10 days, have been observed. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the CAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of chromium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.3 to about 0.5 total moles of silicon and chromium, and from about0.75 to about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing chromium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

PREPARATIVE REAGENTS

CAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare MnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) chromium acetate, and chromium acetate hydroxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

CAPSOs may be prepared by forming a starting solution by dissolving H₃PO₄ in at least part of the water. To this solution the aluminumisopropoxide is added. This mixture is then blended until a homogeneousmixture is observed. To this mixture the silica, the chromium acetate orchromium acetate hydroxide and the templating agent are successivelyadded and at each step the resulting mixture is blended until ahomogeneous mixture is observed.

Alternatively, the water and aluminum isopropoxide may first be mixed,and then the silica, the chromium acetate or chromium acetate hydroxide,the phosphoric acid and the templating agent added, and again at eachstep the resulting mixture is blended until a homogeneous mixture isobserved.

In either case, the mixture is then placed in a line(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogeneous pressure.

GaAPSO MOLECULAR SIEVES

The GaAPSO molecular sieves of U.S. Ser. No. 599,925, filed Apr. 13,1984, and U.S. Ser. No. 845,985 filed Mar. 31, 1986 have a frameworkstructure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.2; and "w", "x","y" and "z" represent the mole fractions of the elements gallium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the GaAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.60          0.38   0.02                                             b       0.38          0.60   0.02                                             c       0.01          0.60   0.39                                             d       0.01          0.39   0.60                                             e       0.39          0.01   0.60                                             f       0.60          0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the GaAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        g       0.45          0.40   0.15                                             h       0.33          0.52   0.15                                             i       0.20          0.52   0.28                                             j       0.20          0.45   0.35                                             k       0.36          0.29   0.35                                             l       0.45          0.29   0.26                                             ______________________________________                                    

GaAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgallium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe GaAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, and preferablyabout 2 to about 15 days, have been observed. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the GaAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of gallium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.5 to about 1.0 total moles of silicon and gallium, and from about 0.75about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing gallium, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

GaAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GaAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) gallium hydroxide, or gallium sulfate;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l): C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

GaAPSOs may be prepared by forming a starting solution by dissolving theH₃ PO₄ in at least part of the water. To this solution the aluminumhydroxide or isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture is added a secondsolution prepared by adding silica to a solution containing the galliumhydroxide and the templating agent and then the combined mixture isblended until a homogeneous mixture is observed.

Alternatively, the templating agent may be added to the solutioncontaining the phosphoric acid and water, and a solution of galliumsulfate in water added, followed by successive additions of silica andaluminum oxide and then the combined mixture is blended until ahomogeneous mixture is observed.

In either case, the mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

GeAPSO MOLECULAR SIEVES

The GeAPSO molecular sieves of U.S. Ser. No. 599,971, filed Apr. 13,1984, and U.S. Ser. No. 852,175 filed Apr. 15, 1986 have a frameworkstructure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ge_(w) Al_(x) P_(y) Si₂)O₂ and has a value of zeroto about 0.3, but is preferably not greater than 0.15; and "w", "x", "y"and "z" represent the mole fractions of the elements germanium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the BeAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.60          0.38   0.02                                             b       0.38          0.60   0.02                                             c       0.01          0.60   0.39                                             d       0.01          0.39   0.60                                             e       0.39          0.01   0.60                                             f       0.60          0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the GeAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        g        0.60         0.35   0.05                                             h        0.47         0.48   0.05                                             i        0.40         0.48   0 12                                             j        0 40         0.36   0.24                                             k        0.46         0.30   0.24                                             l        0.60         0.30   0.10                                             ______________________________________                                    

GeAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgermanium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theGeAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, and preferably about 12hours to about 7 days have been observed. The product is recovered byany convenient method such as centrifugation or filtration.

In synthesizing the GeAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Ge.sub.w Al.sub.x P.sub.y SI.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20, and desirably not greaterthan about 10; and "w", "x", "y" and "z" represent the mole fractions ofgermanium, aluminum, phosphorus and silicon, respectively, and each hasa value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.2 to about 0.3 total moles of silicon and germanium, and from about0.75 to about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing germanium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

PREPARATIVE REAGENTS

GeAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GeAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) germanium tetrachloride or germanium ethoxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TEAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate;

(q) aluminum chlorhydrol.

PREPARATIVE PROCEDURES

In some cases, it may be advantageous, when synthesizing the GeAPSOcompositions, to first combine sources of germanium and aluminum, or ofgermanium, aluminum and silicon, to form a mixed germanium/aluminum orgermanium/aluminum/silicon compound (this compound being typically amixed oxide) and thereafter to combine this mixed compound with a sourceof phosphorus to form the final GaAPSO composition. Such mixed oxidesmay be prepared for example by hydrolyzing aqueous solutions containinggermanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide,tetraethylorthosilicate, and aluminum tri-sec-butoxide.

GeAPSOs may be prepared by forming a starting solution by dissolving theH₃ PO₄ in at least part of the water. To this solution the aluminumisopropoxide or CATAPAL is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture the templating agentand then a solution containing tetraethylorthosilicate and germaniumethoxide, and the resulting mixture blended until a homogeneous mixtureis observed.

Alternatively, the phosphoric acid may first be mixed with thetemplating agent, and then a solution containing tetraethylorthosilicateand germanium ethoxide combined with the phosphoric acid/templatingagent solution. Then the aluminum oxide is added and the resultantmixture blended until homogeneous.

In a third procedure, the phosphoric acid may first be mixed with thetemplating agent and water, and to the resultant solution is added thesolid aluminum/silicon/germanium mixed oxide prepared as describedabove. The resultant mixture is then blended until homogeneous.

Whichever procedure is adopted, the final mixture is then placed in alined (polytetrafluoroethylene) stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C.) for a time or placed inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

LiAPSO MOLECULAR SIEVES

The LiAPSO molecular sieves of U.S. Ser. No. 599,952, filed Apr. 13,1984, and U.S. Ser. No. 847,227 filed Apr. 2, 1986 have a frameworkstructure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements lithium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the LiAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.38   0.02                                             b        0.38         0.60   0.02                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the LiAPSO molecular sieves, thevalue of w+z is not greater than about 0.20.

Since the exact nature of the LiAPSO molecular sieves is not clearlyunderstood at present, although all are believed to contain LiO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the LiAPSO molecularsieves by means of their chemical composition. This is due to the lowlevel of lithium present in certain of the LiAPO molecular sievesprepared to date which makes it difficult to ascertain the exact natureof the interaction between lithium, aluminum phosphorus and silicon. Asa result, although it is believed that LiO₂ tetrahedra are substitutedisomorphously for AlO₂, PO₂ or SiO₂ tetrahedra, it is appropriate tocharacterize certain LiAPSO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

LiAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources oflithium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theLiAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the LiAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not moe than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20, and most desirably notgreater than about 10; and "w", "x", "y" and "z" represent the molefractions of lithium, aluminum, phosphorus and silicon, respectively,and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing lithium, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

PREPARATIVE REAGENTS

LiAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare LiAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) lithium orthophosphate;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) c-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

PREPARATIVE PROCEDURES

LiAPSOs may be prepared by forming a starting reaction mixture mixinglithium phosphate and aluminum oxide, then adding the resultant mixtureto the H₃ PO₄. To the resultant mixture is added silica and thetemplating agent and the resulting mixture is blended until ahomogeneous mixture is observed. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

MeAPO MOLECULAR SIEVES

MeAPO molecular sieves are crystalline microporous aluminophosphates inwhich the substituent metal is one of a mixture of two or more divalentmetals of the group magnesium, manganese, zinc and cobalt and aredisclosed in U.S. Pat. No. 4,567,029. Members of this novel class ofcompositions have a three-dimensional microporous crystal frameworkstructure of MO₂ ⁻², AlO⁻ ₂ and PO⁺ ₂ tetrahedral units and have anessential empirical chemical composition, on an anhydrous basis, of:

    mR:(M.sub.x Al.sub.y P.sub.z)0.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular metal aluminophosphate involved; "x", "y",and "z" represent the mole fractions of the metal "M", (i.e., magnesium,manganese, zinc and cobalt), aluminum and phosphorus, respectively,present as tetrahedral oxides, said mole fractions being such that theyare representing the following values for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.35           0.05   0.60                                           D        0.35           0.60   0.05                                           ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.In a preferred subclass of the metal aluminophosphates of thisinvention, the values of "x", "y" and "z" in the formula above arerepresenting the following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.52   0.47                                           b        0.01           0.39   0.60                                           c        0.25           0.15   0.60                                           d        0.25           0.40   0.35                                           ______________________________________                                    

The as-synthesized compositions are capable of withstanding 350° C.calcination in air for extended periods, i.e., at least 2 hours, withoutbecoming amorphous. While it is believed that the M, Al and P frameworkconstituents are present in tetrahedral coordination with oxygen, it istheoretically possible that some minor fraction of these frameworkconstituents are present in coordination with five or six oxygen atoms.It is not, moreover, necessarily the case that all of the M, Al and/or Pcontent of any given synthesized product is a part of the framework inthe aforesaid types of coordination with oxygen. Some of eachconstituent may be merely occluded or in some as yet undetermined formand may or may not be structurally significant.

Since the term "metal aluminophosphate" is somewhat cumbersome,particularly in view of the need for numerous repetitions thereof indescribing such compositions, the "short-hand" reference "MeAPO" isemployed hereinafter. Also in those cases where the metal "Me" in thecomposition is magnesium, the acronym MAPO is applied to thecomposition. Similarly, ZAPO, MnAPO, and CoAPO are applied to thecompositions which contain zinc, manganese and cobalt, respectively. Toidentify the various structural species which make up each of thesubgeneric classes MAPO, ZAPO, CoAPO and MnAPO, each species is assigneda number and is identified, for example, as ZAPO-5, MAPO-11, CoAPO-11and so forth.

The term "essential empirical chemical composition" is meant to includethe crystal framework and can include any organic templating agentpresent in the pore system, but does not include alkali metal or otherions which can be present by virtue of being contained in the reactionmixture or as a result of post-synthesis ion-exchange. Such ionicspecies, when present, function primarily as charge-balancing ions forAlO₂ ⁻ and/or MO₂ ⁻² tetrahedra not associated with PO₂ ⁺ tetrahedra oran organic ion derived from the organic templating agent.

The metal aluminophosphates ("MeAPOs") are synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe metal "M", alumina and phosphate, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure at a temperature between 100° C.and 225° C., and preferably between 100° C. and 200° C., until crystalsof the metal aluminophosphate product are obtained, usually a period offrom 4 hours to 2 weeks. The product is recovered by any convenientmethod such as centrifugation or filtration.

In synthesizing the MeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of molar ratios asfollows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" has a value great enoughto constitute an effective concentration of "R" and is within the rangeof >0 to 6; "b" has a value of from zero to 500, preferably 2 to 30; "M"represents a metal of the group zinc, magnesium, manganese and cobalt,"x", "y" and "z" represent the mole fractions, respectively, of "M",aluminum and phosphorus in the (M_(x) Al_(y) P_(z))O₂ constituent, andeach has a value of at least 0.01, the said points E, F, G, H, I, and Jrepresenting the following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        E        0.01           0.70   0.29                                           F        0.01           0.29   0.70                                           G        0.29           0.01   0.70                                           H        0.40           0.01   0.59                                           I        0.40           0.59   0.01                                           J        0.29           0.70   0.01                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (M+Al+P)=(x+y+z)=1.00 mole.

In forming the reaction mixture from which the metal aluminophosphatesare crystallized the organic templating agent can be any of thoseheretofore proposed for use in the synthesis of conventional zeolitealuminosilicates and microporous aluminophosphates. In general thesecompounds contain elements of Group VA of the Periodic Table ofElements, particularly nitrogen, phosphorus, arsenic and antimony,preferably N or P and most preferably N, which compounds also contain atleast one alkyl or aryl group having from 1 to 8 carbon atoms.Particularly preferred nitrogen-containing compounds for use astemplating agents are the amines and quaternary ammonium compounds, thelatter being represented generally by the formula R₄ N⁺ wherein each Ris an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymericquaternary ammonium salts such as [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x"has a value of at least 2 are also suitably employed. Both mono-, di-and triamines are advantageously utilized, either alone or incombination with a quaternary ammonium compound or other templatingcompound. Mixtures of two or more templating agents can either producemixtures of the desired metal aluminophosphates or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; di-n-propylamine; tripropylamine;triethylamine; triethanolamine; piperidine; cyclohexylamine;2-methylpyridine; N,N-dimethylbenzylamine; N-N-dimethylethanolamine;choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane;N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine;3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine;4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine;isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and2-imidazolidone. Not every templating agent will direct the formation ofevery species of metal aluminophosphate (MeAPO), i.e., a singletemplating agent can, with proper manipulation of the reactionconditions, direct the formation of several MeAPO compositions, and agiven MeAPO composition can be produced using several differenttemplating agents.

The preferred phosphorus source is phosphoric acid, but organicphosphates such as triethylphosphate have been found satisfactory, andso also have crystalline or amorphous aluminophosphates such as theAlPO₄ composition of U.S. Pat. No. 4,310,440. Organo-phosphoruscompounds, such as tetrabutylphosphonium bromide do not, apparentlyserve as reactive sources of phosphorus, but these compounds do functionas templating agents. Conventional phosphorus salts such as sodiummetaphosphate, may be used, at least in part, as the phosphorus source,but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isopropoxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The metals zinc, cobalt, magnesium and manganese can be introduced intothe reaction system in any form which permits the formation in situ ofreactive divalent ions of the respective metals. Advantageously salts,oxides or hydroxides of the metals are employed such as cobalt chloridehexahydrate, alpha cobaltous iodide, cobaltous sulfate, cobalt acetate,cobaltous bromide, cobaltous chloride, zinc acetate, zinc bromide, zincformate, zinc iodide, zinc sulfate heptahydrate, magnesium acetate,magnesium bromide, magnesium chloride, magnesium iodide, magnesiumnitrage, magnesium sulfate, manganous acetate, manganous bromide,manganous sulfate, and the like.

While not essential to the synthesis of MeAPO compositions, it has beenfound that in general, stirring or other moderate agitation of thereaction mixture and/or seeding the reaction mixture with seed crystalsof either the MeAPO species to be produced or a topologically similaraluminophosphate or aluminosilicate composition, facilitates thecrystallization procedure.

After crystallization the MeAPO product is isolated and advantageouslywashed with water and dried in air. The as-synthesized MeAPO containswithin its internal pore system at least one form of the templatingagent employed in its formation. Most commonly the organic moiety ispresent, at least in part, as a charge-balancing cation as is generallythe case with as-synthesized aluminosilicate zeolites prepared fromorganic-containing reaction systems. It is possible, however, that someor all of the organic moiety is an occluded molecular species in aparticular MeAPO species. As a general rule, the templating agent, andhence the occluded organic species, is too large to move freely throughthe pore system of the MeAPO product and must be removed by calciningthe MeAPO at temperatures of 200° C. to 700° C. to thermally degrade theorganic species. In a few instances the pores of the MeAPO product aresufficiently large to permit transport of the templating agent,particularly if the latter is a small molecule, and accordingly completeor partial removal thereof can be accomplished by conventionaldesorption procedures such as carried out in the case of zeolites. Itwill be understood that the term "as-synthesized" as used herein doesnot include the condition of the MeAPO phase wherein the organic moietyoccupying the intracrystalline pore system as a result of thehydrothermal crystallization process has been reduced by post-synthesistreatment such that the value of "m" in the composition formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an aluminum alkoxideis employed as the source of aluminum, the corresponding alcohol isnecessarily present in the reaction mixture since it is a hydrolysisproduct of the alkoxide. It has not been determined whether this alcoholparticipates in the synthesis process as a templating agent. For thepurposes of this application, however, this alcohol is arbitrarilyomitted from the class of templating agents, even if it is present inthe as-synthesized MeAPO material.

Since the MeAPO compositions are formed from AlO₂, PO₂, and MO₂tetrahedral units which, respectively, have a net charge of -1, +1, and-2, the matter of cation exchangeability is considerably morecomplicated than in the case of zeolitic molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ tetrahedraand charge-balancing cations. In the MeAPO compositions, an AlO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such s an alkali metal cation, acation of the metal "M" present in the reaction mixture, or an organiccation derived from the templating agent. Similarly an MO₂ ⁻²tetrahedron can be balanced electrically by association with PO₂ ⁺tetrahedra, a cation of the metal "M", organic cations derived from thetemplating agent, or other divalent or polyvalent metal cationsintroduced from an extraneous source. It has also been postulated thatnon-adjacent AlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺and OH⁻, respectively [Flanigen and Grose, Molecular Sieve Zeolites-I,ACS, Washington, D.C. (1971)].

FAPO MOLECULAR SIEVES

Ferroaluminophosphates are disclosed in U.S. Pat. No. 4,554,143,incorporated herein by reference, and have a three-dimensionalmicroporous crystal framework structure of AlO₂, FeO₂, and PO₂tetrahedral units and have an essential empirical chemical composition,on an anhydrous basis, of:

    mR: (Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular ferroaluminophosphate involved; "x", "y",and "z" represent the mole fractions of iron, aluminum and phosphorus,respectively, present as tetrahedral oxides, representing the followingvalues for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.35           0.05   0.60                                           D        0.35           0.60   0.05                                           ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.In a preferred subclass of the ferroaluminophosphates the values of "x","y" and "z" in the formula above are representing the following valuesfor "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.52   0.47                                           b        0.01           0.39   0.60                                           c        0.25           0.15   0.60                                           d        0.25           0.40   0.35                                           ______________________________________                                    

The iron of the FeO₂ structural units can be in either the ferric orferrous valence state, depending largely upon the source of the iron inthe synthesis gel. Thus, an FeO₂ tetrahedron in the structure can have anet charge of either -1 or -2. While it is believed that the Fe, Al andP framework constituents are present in tetrahedral coordination withoxygen (and are referred to herein as such), it is theoreticallypossible that some minor fraction of these framework constituents arepresent in coordination with five or six oxygen atoms. It is not,moreover, necessarily the case that all of the Fe, Al and/or P contentof any given synthesized product is a part of the framework in theaforesaid types of coordination with oxygen. Some of each constituentmay be merely occluded or in some as yet undetermined form, and may ormay not be structurally significant.

For convenience in describing the ferroaluminophosphates, the"short-hand" acronym "FAPO" is sometimes employed hereinafter. Toidentify the various structural species which make up the generic classFAPO, each species is assigned a number and is identified, for example,as FAPO-11, FAPO-31 and so forth.

The term "essential empirical chemical composition" is meant to includethe crystal framework and can include any organic templating agentpresent in the pore system, but does not include alkali metal or otherirons which can be present by virtue of being contained in the reactionmixture or as a result of post-synthesis ion-exchange. Such ionicspecies, when present, function primarily as charge-balancing ions forFeO₂ ⁻ and/or AlO₂ ⁻² tetrahedra, FeO₂ ⁻² tetrahedra associated with PO₂⁺ tetrahedra or not associated with PO₂ ⁺ tetrahedra or an organic ionderived from the organic templating agent.

The aforesaid ferroaluminophosphates are synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofiron oxide, alumina and phosphate, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure at a temperature of at least 100°C., and preferably between 100° C. and 250° C., until crystals of themetal aluminophosphate product are obtained, usually a period of from 2hours to 2 weeks. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the FAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of molar ratios asfollows:

    aR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" has a value great enoughto constitute an effective concentration of "R" and is within the rangeof >0 to 6; "b" has a value of from zero to 500, preferably 2 to 80;"x", "y" and "z" represent the mole fractions, respectively, of iron,aluminum and phosphorus in the (Fe_(x) Al_(y) P_(z))O₂ constituent, andeach has a value of at least 0.01, and representing the following valuesfor "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        E        0.01           0.70   0.29                                           F        0.01           0.29   0.70                                           G        0.29           0.01   0.70                                           H        0.40           0.01   0.59                                           I        0.40           0.59   0.01                                           J        0.29           0.70   0.01                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (Fe+Al+P)=(x+y+z)=1.00 mole.

In forming the reaction mixture from which the ferroaluminophosphatesare crystallized, the organic templating agent can be any of thoseheretofore proposed for use in the synthesis of conventional zeolitealuminosilicates and microporous aluminophosphates. In general thesecompounds contain elements of Group VA of the Periodic Table ofElements, particularly nitrogen, phosphorus, arsenic and antimony,preferably N or P and most preferably N, which compounds also contain atleast one alkyl or aryl group having from 1 to 8 carbon atoms.Particularly preferred nitrogen-containing compounds for use astemplating agents are the amines and quaternary ammonium compounds, thelatter being represented generally by the formula R₄ N⁺ wherein each Ris an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymericquaternary ammonium salts such as [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x"has a value of at least 2 are also suitably employed. Mono-, di- andtriamines are advantageously utilized, either alone or in combinationwith a quaternary ammonium compound or other templating compound.Mixtures of two or more templating agents can either produce mixtures ofthe desired metal aluminophosphates or the more strongly directingtemplating species may control the course of the reaction with the othertemplating species serving primarily to establish the pH conditions ofthe reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; di-n-propylamine; tri-n-propylamine;triethylamine; triethanolamine; piperidine; cyclohexylamine;2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine;choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane;N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine;3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine;4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2)octane ion; di-n-butylamine; neopentylamine; di-n-pentylamine;isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and2-imidazolidone. Not every templating agent will direct the formation ofevery species of ferroaluminophosphate (FAPO), i.e., a single templatingagent can, with proper manipulation of the reaction conditions, directthe formation of several FAPO compositions, and a given FAPO compositioncan be produced using several different templating agents.

The phosphorus source is preferably phosphoric acid, but organicphosphates such as triethylphosphate have been found satisfactory, andso also have crystalline or amorphous aluminophosphates such as theAlPO₄ composition of U.S. Pat. No. 4,310,440. Organo-phosphoruscompounds, such as tetrabutylphosphonium bromide do not, apparentlyserve as reactive sources of phosphorus, but these compounds do functionas templating agents. Conventional phosphorus salts such as sodiummetaphosphate, may be used, at least in part, as the phosphorus source,but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isopropoxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

Iron can be introduced into the reaction system in any form whichpermits the formation in situ of reactive ferrous or ferric ions.Advantageously iron salts, oxides or hydroxides are employed such asiron sulfate, iron acetate, iron nitrate, or the like. Other sourcessuch as a freshly precipitated iron oxide τ-FeOOH, are also suitable.

While not essential to the synthesis of FAPO compositions, it has beenfound that in general, stirring or other moderate agitation of thereaction mixture and/or seeding the reaction mixture with seed crystalsof either the FAPO species to be produced or a topologically similaraluminophosphate or aluminosilicate composition, facilitates thecrystallization procedure.

After crystallization the FAPO product is isolated and advantageouslywashed with water and dried in air. The as-synthesized FAPO containswithin its internal pore system at least one form of the templatingagent employed in its formation. Most commonly the organic moiety ispresent, at least in part, as a charge-balancing cation as is generallythe case with as-synthesized aluminosilicate zeolites prepared fromorganic-containing reaction systems. It is possible, however, that someor all of the organic moiety is an occluded molecular species in aparticular FAPO species. As a general rule, the templating agent, andhence the occluded organic species, is too large to move freely throughthe pore system of the FAPO product and must be removed by calcining theFAPO at temperatures of 200° C. to 700° C. to thermally degrade theorganic species. In a few instances the pores of the FAPO product aresufficiently large to permit transport of the templating agent,particularly if the latter is a small molecule, and accordingly completeor partial removal thereof can be accomplished by conventionaldesorption procedures such as carried out in the case of zeolites. Itwill be understood that the term "as-synthesized" as used herein and inthe claims does not include the condition of the FAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula:

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an aluminum alkoxideis employed as the source of aluminum, the corresponding alcohol isnecessarily present in the reaction mixture since it is a hydrolysisproduct of the alkoxide. It has not been determined whether this alcoholparticipates in the syntheses process as a templating agent. For thepurposes of this application, however, this alcohol is arbitrarilyomitted from the class of templating agents, even if it is present inthe as-synthesized FAPO material.

Since the FAPO compositions are formed from AlO₂ ⁻, PO₂ ⁺, FeO₂ ⁻ and/orFeO₂ ⁻² units the matter of cation exchangeability is considerably morecomplicated than in the case of zeolitic molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ tetrahedraand charge-balancing cations. In the FAPO compositions, an AlO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, aFe⁺² or Fe⁺³ cation present in the reaction mixture, or an organiccation derived from the templating agent. Similarly an FeO₂ ⁻ or FeO₂ ⁻²tetrahedron can be balanced electrically by association with PO₂ ⁺tetrahedron, a Fe⁺² or Fe⁺³ cation, organic cations derived from thetemplating agent, or other metal cation introduced from an extraneoussource. It has also been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺tetrahedral pairs can be balanced by Na⁺ and OH⁻, respectively [Flanigenand Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].

TAPO MOLECULAR SIEVES

TAPO molecular sieves are disclosed in U.S. Pat. No. 4,500,561,incorporated herein by reference, and comprise a three-dimensionalmicroporous crystal framework structure of [TiO₂ ], [AlO₂ ] and [PO₂ ]tetrahedral units which has a unit empirical formula on an anhydrousbasis of:

    mR: (Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of betweenzero and about 5.0, the maximum value in each case depending upon themolecular dimensions of the templating agent and the available voidvolume of pore system of the particular titanium molecular sieve; "x","y" and "z" represent the mole fractions of titanium, aluminum andphosphorus, respectively, present as tetrahedral oxides, representingthe following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.001         0.45   0.549                                           B        0.88          0.01   0.11                                            C        0.98          0.01   0.01                                            D        0.29          0.70   0.01                                            E        0.001         0.70   0.299                                           ______________________________________                                    

The parameters "x", "y" and "z" are preferably within the followingvalues for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y       z                                              ______________________________________                                        a        0.002         0.499   0.499                                          b        0.20          0.40    0.40                                           c        0.20          0.50    0.30                                           d        0.10          0.60    0.30                                           e        0.002         0.60    0.398                                          ______________________________________                                    

The titanium-containing molecular sieves are referred to hereinafter,solely for point of reference herein as "TAPO" molecular sieves, or as"TAPOs" if the reference is to the class as a whole. This designation issimply made for the sake of convenient reference herein and is not meantto designate a particular structure for any given TAPO molecular sieve.The members of the class of TAPO's employed hereinafter in the exampleswill be characterized simply by referring to such members as TAPO-5,TAPO-11, etc, i.e., a particular species will be referred to as TAPO-nwhere "n" is a number specific to a given class member as itspreparation is reported herein. This designation is an arbitrary one andis not intended to denote structural relationship to another material(s)which may also be characterized by a numbering system.

The term "unit empirical formula" is used herein according to its commonmeaning to designate the simplest formula which gives the relativenumber of moles of titanium, aluminum and phosphorus which form the[TiO₂ ], [PO₂ ] and [AlO₂ ] tetrahedral unit within atitanium-containing molecular sieve and which forms the molecularframework of the TAPO composition(s). The unit empirical formula isgiven in terms of titanium, aluminum and phosphorus as shown in Formula(1), above, and does not include other compounds, cations or anionswhich may be present as a result of the preparation or the existence ofother impurities or materials in the bulk composition not containing theaforementioned tetrahedral unit. The amount of template R is reported aspart of the composition when the as-synthesized unit empirical formulais given, and water may also be reported unless such is defined as theanhydrous form. For convenience, coefficient "m" for template "R" isreported as a value that is normalized by dividing the number of molesof organic templating agent by the total moles of titanium, aluminum andphosphorus.

The unit empirical formula for a TAPO may be given on an"as-synthesized" basis or may be given after an "as-synthesized" TAPOcomposition has been subjected to some post treatment process, e.g.,calcination. The term "as-synthesized" herein shall be used to refer tothe TAPO composition(s) formed as a result of the hydrothermalcrystallization but before the TAPO composition has been subjected topost treatment to remove any volatile components present therein. Theactual value of "m" for a post-treated TAPO will depend on severalfactors (including: the particular TAPO, template, severity of thepost-treatment in terms of its ability to remove the template from theTAPO, the proposed application of the TAPO composition, and etc.) andthe value for "m" can be within the range of values as defined for theas-synthesized TAPO compositions although such is generally less thanthe as-synthesized TAPO unless such post-treatment process adds templateto the TAPO so treated. A TAPO composition which is in the calcined orother post-treatment form generally has an empirical formula representedby Formula (1), except that the value of "m" is generally less thanabout 0.02. Under sufficiently severe post-treatment conditions, e.g.,roasting in air at high temperature for long periods (over 1 hr.), thevalue of "m" may be zero (0) or, in any event, the template, R, isundetectable by normal analytical procedures.

The TAPO molecular sieves are generally further characterized by anintracrystalline adsorption capacity for water at 4.6 torr and about 24°C. of about 3.0 weight percent. The adsorption of water has beenobserved to be completely reversible while retaining the same essentialframework topology in both the hydrated and dehydrated state. The term"essential framework topology" is meant to designate the spatialarrangement of the primary bond linkages. A lack of change in theframework topology indicates that there is no disruption of theseprimary bond linkages.

The TAPO molecular sieves are generally synthesized by hydrothermalcrystallization from a reaction mixture comprising reactive sources oftitanium, aluminum and phosphorus, and one or more organic templatingagents. Optionally, alkali metal(s) may be present in the reactionmixture. The reaction mixture is placed in a pressure vessel, preferablylined with an inert plastic material, such as polytetrafluoroethylene,and heated, preferably under autogenous pressure, at a temperature of atleast about 100° C., and preferably between 100° C. and 250° C., untilcrystals of the molecular sieve product are obtained, usually for aperiod of from 2 hours to 2 weeks. While not essential to the synthesisof the TAPO molecular sieves, it has been found that in general stirringor other moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the TAPO to be produced,or a topologically similar composition, facilitates the crystallizationprocedure. The product is recovered by any convenient method such ascentrifugation or filtration.

After crystallization the TAPO(s) may be isolated and washed with waterand dried in air. As a result of the hydrothermal crystallization, theas-synthesized TAPO contains within its intracrystalline pore system atleast one form of the template employed in its formation. Generally, thetemplate is a molecular species, but it is possible, stericconsiderations permitting, that at least some of the template is presentas a charge-balancing cation. Generally the template is too large tomove freely through the intracrystalline pore system of the formed TAPOand may be removed by a post-treatment process, such as by calcining theTAPO at temperatures of between about 200° C. and to about 700° C. so asto thermally degrade the template or by employing some otherpost-treatment process for removal of at least part of the template fromthe TAPO. In some instances the pore of the TAPO are sufficiently largeto permit transport of the template, and, accordingly, complete orpartial removal thereof can be accomplished by conventional desorptionprocedures such as carried out in the case of zeolites.

The TAPOs are preferably formed from a reaction mixture having a molefraction of alkali metal cation which is sufficiently low that it doesnot interfere with the formation of the TAPO composition. The TAPOcompositions are generally formed from a reaction mixture containingreactive sources of TiO₂, Al₂ O₃, and P₂ O₅ and an organic templatingagent, said reaction mixture comprising a composition expressed in termsof molar oxide ratios of:

    fR.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :g H.sub.2 O

wherein "R" is an organic templating agent; "f" has a value large enoughto constitute an effective amount of "R", said effective amount beingthat amount which form said TAPO compositions; "g" has a value of fromzero to 500; "x", "y" and "z" represent the mole fractions, respectivelyof titanium, aluminum and phosphorus in the (Ti_(x) Al_(y) P_(z))O₂constituent, and each has a value of at least 0.001 and being within thefollowing values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y       z                                              ______________________________________                                        h        0.001         0.989   0.01                                           i        0.001         0.01    0.989                                          j        0.32          0.24    0.44                                           k        0.98          0.01    0.01                                           ______________________________________                                    

Although the TAPO compositions will form if higher concentrations ofalkali metal cation are present, such reaction mixtures are notgenerally preferred. A reaction mixture, expressed in terms of molaroxide ratios, comprising the following bulk composition is preferred:

    oR.sub.2 O:wM.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :nH.sub.2 O

wherein "R" is an organic template; "o" has a value great enough toconstitute an effective concentration of "R" and is preferably withinthe range of from greater than zero (0) to about 5.0; "M" is an alkalimetal cation; "w" has a value of from zero to 2.5; "n" has a valuebetween about zero (0) and about 500; "x", "y" and "z" represent themole fractions, respectively, of titanium, aluminum and phosphorus inthe (Ti_(x) Al_(y) P_(z))O₂ constituent, and each has a value of atleast 0.001 and being within the following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y       z                                              ______________________________________                                        h        0.001         0.989   0.01                                           i        0.001         0.01    0.989                                          j        0.32          0.24    0.44                                           k        0.98          0.01    0.01                                           ______________________________________                                    

When the TAPOs are synthesized by this method the value of "m" in theFormula above is generally above about 0.02.

Though the presence of alkali metal cations is not preferred, when theyare present in the reaction mixture it is preferred to first admix atleast a portion (e.g., at least about 10 weight percent) of each of thealuminum and phosphorus sources in the substantial absence (e.g.,preferably less than about 20 percent of the total weight of thealuminum source and phosphorus source) of the titanium source. Thisprocedure avoids adding the phosphorus source to a basic reactionmixture containing the titanium source and aluminum source, (as was donein most of the published attempts to substitute isomorphously [PO₂ ]tetrahedra for [SiO₂ ] tetrahedra in zeolitic structures). Although thereaction mechanism is by no means clear at this time, the function ofthe template may be to favor the incorporation of [PO₂ ] and [AlO₂ ]tetrahedra in the framework structures of the crystalline products with[TiO₂ ] tetrahedra isomorphously replacing [PO₂ ] tetrahedra.

The reaction mixture from which these TAPOs are formed contains one ormore organic templating agents (templates) which can be most any ofthose heretofore proposed for use in the synthesis of aluminosilicatesand aluminophosphates. The template preferably contains at least oneelement of Group VA of the Periodic Table, particularly nitrogen,phosphorus, arsenic and/or antimony, more preferably nitrogen orphosphorus and most preferably nitrogen and is desirably of the formulaR₄ X⁺ wherein X is selected from the group consisting of nitrogen,phosphorus, arsenic and/or antimony and R may be hydrogen, alkyl, aryl,aralkyl, or alkylaryl group and is preferably aryl or alkyl containingbetween 1 and 8 cabon atoms, although more than eight carbon atoms maybe present in the group "R" of the template. Nitrogen-containingtemplates are preferred, including amines and quaternary ammoniumcompounds, the latter being represented generally by the formula R'₄ N⁺wherein each R' is an alkyl, aryl, alkylaryl, or aralkyl group; whereinR' preferably contains from 1 to 8 carbon atoms or higher when R' isalkyl and greater than 6 carbon atoms when R' is otherwise, ashereinbefore discussed. Polymeric quaternary ammonium salts such as[(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 may alsobe employed. The mono-, di- and triamines, including mixed amines, mayalso be employed as templates either alone or in combination with aquaternary ammonium compound or another template. The exact relationshipof various templates when concurrently employed is not clearlyunderstood. Mixtures of two or more templating agents can produce eithermixtures of TAPOs or in the instance where one template is more stronglydirecting than another template the more strongly directing template maycontrol the course of the hydrothermal crystallization wherein with theother template serving primarily to establish the pH conditions of thereaction mixture.

Representative templates include tetramethylammonium,tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions;di-n-propylamine; tripropylamine; triethylamine; triethanolamine;piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-diethylethanolamine; dicyclohexylamine; N,N-dimethylethanolamine;1,4-diazabicyclo(2,2,2)octane; N-methyldiethanolamine,N-methyl-ethanolamine; N-methylcyclohexylamine; 3-methyl-pyridine;4-methylpyridine; quinuclidine;N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine;neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine;ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templatewill produce every TAPO composition although a single template can, withproper selection of the reaction conditions, cause the formation ofdifferent TAPO compositions, and a given TAPO composition can beproduced using different templates.

In those instances where an aluminum alkoxide is the reactive aluminumsource, the corresponding alcohol is necessarily present in the reactionmixture since it is a hydrolysis product of the alkoxide. It has not asyet been determined whether this alcohol participates in the synthesisprocess as a templating agent, or in some other function and,accordingly, is not reported as a template in the unit formula of theTAPOs, although such may be acting as templates.

Alkali metal cations, if present in the reaction mixture, may facilitatethe crystallization of certain TAPO phases, although the exact functionof such cations, when present, in crystallization, if any, is notpresently known. Alkali cations present in the reaction mixturegenerally appear in the formed TAPO composition, either as occluded(extraneous) cations and/or as structural cations balancing net negativecharges at various sites in the crystal lattice. It should be understoodthat although the unit formula for the TAPOs does not specificallyrecite the presence of alkali cations they are not excluded in the samesense that hydrogen cations and/or hydroxyl groups are not specificallyprovided for in the traditional formulae for zeolitic aluminosilicates.

Almost any reactive titanium source may be employed herein. Thepreferred reactive titanium sources include titanium alkoxides,water-soluble titanates and titanium chelates.

Almost any reactive phosphorus source may be employed. Phosphoric acidis the most suitable phosphorus source employed to date. Accordingly,other acids of phosphorus are generally believed to be suitablephosphorus sources for use herein. Organic phosphates such as triethylphosphate have been found satisfactory, and so also have crystalline oramorphous aluminophosphates such as the AlPO₄ compositions of U.S. Pat.No. 4,310,440. Organo-phosphorus compounds, such astetrabutyl-phosphonium bromide have not, apparently, served as reactivesources of phosphorus, but these compounds do function as templatingagents and may also be capable of being suitable phosphorus sourcesunder proper process conditions (yet to be ascertained). Organicphosphorus compounds, e.g., esters, are believed to be generallysuitable since they can generate acids of phosphorus in situ.Conventional phosphorus salts, such as sodium metaphosphate, may beused, at least in part as the phosphorus source, but they are notpreferred.

Almost any reactive aluminum source may be employed herein. Thepreferred reactive aluminum sources include aluminum alkoxides, such asaluminum isopropoxide, and pseudoboehmite. Crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but as generally not preferred.

Since the exact nature of the TAPO molecular sieves are not clearlyunderstood at present, although all are believed to contain [TiO₂ ]tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the TAPO molecular sievesby means of their chemical composition. This is due to the low level oftitanium present in certain of the TAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between titanium, aluminum and phosphorus. As a result,although it is believed that titanium, [TiO₂ ], has substitutedisomorphously for [AlO₂ ] or [PO₂ ] tetrahedra, it is appropriate tocharcterize certain TAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides in the as-synthesizedand anhydrous form as:

    vR:pTiO.sub.2 :qAl.sub.2 O.sub.3 :rP.sub.2 O.sub.5

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "v" represents an effective amount ofthe organic templating agent to form said TAPO compositions andpreferably has a value between and including zero and about 3.0; "p","q" and "r" represent moles, respectively, of titanium, alumina andphosphorus pentoxide, based on said moles being such that they arewithin the following values for "p", "q" and "r":

    ______________________________________                                               Mole Fraction                                                          Point    x             y     z                                                ______________________________________                                        A        0.004         1.0   1.22                                             B        176           1.0   11.0                                             C        196           1.0   1.0                                              D        0.828         1.0   0.0143                                           E        0.003         1.0   0.427                                            ______________________________________                                    

The parameters "p", "q" and "r" are preferably within the followingvalues for "p", "q" and "r":

    ______________________________________                                               Mole Fraction                                                          Point    x              y     z                                               ______________________________________                                        a        0.008          1.0   1.0                                             b        1.0            1.0   1.0                                             c        0.80           1.0   0.60                                            d        0.333          1.0   0.50                                            e        0.067          1.0   0.663                                           ______________________________________                                    

ELAPO MOLECULAR SIEVES

"ELAPO" molecular sieves are a class of crystalline molecular sieves inwhich at least one element capable of forming a three-dimensionalmicroporous framework forms crystal framework structures of AlO₂ ⁻, PO₂⁺ and MO₂ ^(n) tetrahedral oxide units wherein "MO₂ ^(n) " represents atleast one different element (other than Al or P) present as tetrahedraloxide units "MO₂ ^(n) " with charge "n" where "n" may be -3, -2, -1, 0or +1. The members of this novel class of molecular sieve compositionshave crystal framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ ; "M" represents at least oneelement capable of forming framework tetrahedral oxides; and "x", "y"and "z" represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides. "M" is at least onedifferent (i.e., not aluminum, phosphorus or oxygen) element such thatthe molecular sieves contain at least one framework tetrahedral unit inaddition to AlO₂ ⁻ and PO₂ ⁺. "M" is at least one element selected fromthe group consisting of arsenic, beryllium, boron, cobalt, chromium,gallium, germanium, iron, lithium, magnesium, manganese, titanium andzinc, subject to certain restrictions on the combinations of elements aswill appear from the discussions of individual groups of ELAPOs below.ELAPOs and their preparation are disclosed in European PatentApplication Ser. No. 85104386.9, filed Apr. 11, 1985 (EPC PublicationNo. 0158976, published Oct. 13, 1985, incorporated herein by reference)and 85104388.5, filed Apr. 11, 1985 (EPC Publication No. 158349,published Oct. 16, 1985, incorporated herein by reference).

The "ELAPO" molecular sieves further include numerous species which areintended herein to be within the scope of the term "non-zeoliticmolecular sieves" such being disclosed in the following copending andcommonly assigned applications, incorporated herein by reference thereto[(A) following a serial number indicates that the application isabandoned, while (CIP) following a serial number indicates that theapplication is a continuation-in-part of the immediately precedingapplication, and (C) indicates that the application is a continuation ofthe immediately preceding application]:

    ______________________________________                                        U.S. Ser. No.                                                                             Filed            NZMS                                             ______________________________________                                        600,166(A)  April 13, 1984   AsAPO                                            830,889(CIP)                                                                              Feb. 19, 1986    AsAPO                                            599,812(A)  April 13, 1984   BAPO                                             804,248(C)(A)                                                                             Dec. 4, 1985     BAPO                                             29,540(CIP) March 24, 1987   BAPO                                             599,776(A)  April 13, 1984   BeAPO                                            835,293(CIP)                                                                              March 3, 1986    BeAPO                                            599,813(A)  April 13, 1984   CAPO                                             830,756(CIP)                                                                              Feb. 19, 1986    CAPO                                             599,771(A)  April 13, 1984   GaAPO                                            830,890(CIP)                                                                              Feb. 19, 1986    GaAPO                                            599,807(A)  April 13, 1984   GeAPO                                            841,753(CIP)                                                                              March 20, 1986   GeAPO                                            599,811(A)  April 13, 1984   LiAPO                                            834,921(CIP)                                                                              Feb. 28, 1986    LiAPO                                            600,171     April 13, 1984   FCAPO                                            (now U.S. Pat. No. 4,686,093 issued August 11, 1987)                          600,172(A)  April 13, 1984       ElAPO (M                                                                      comprises two                                                                 different                                    846.088(CIP)                                                                              March 31, 1986       elements)                                    599,824(A)  April 13, 1984       FeTiAPO                                      902,129(C)  September 2, 1986    FeTiAPO                                      599,810(A)  April 13, 1984       XAPO                                         902,020(C)  September 2, 1986    XAPO                                         ______________________________________                                    

The ELAPO molecular sieves are generally referred to herein by theacronym "ELAPO" to designate element(s) "M" in a framework of AlO₂ ⁻,PO₂ ⁺ and MO₂ ^(n) tetrahedral oxide units. Actual class members will beidentified by replacing the "EL" of the acronym with the elementspresent as MO₂ ^(n) tetrahedral units. For example, "MgBeAPO" designatesa molecular sieve comprised of AlO₂ ⁻, PO₂ ⁺, MgO₂ ⁻² and BeO₂ ⁻²tetrahedral units. To identify various structural species which make upeach of the subgeneric classes, each species is assigned a number and isidentified as "ELAPO-i" wherein "i" is an integer. The given speciesdesignation is not intended to denote a similarity in structure to anyother species denominated by a similar identification system.

The ELAPO molecular sieves comprise at least one additional elementcapable of forming framework tetrahedral oxide units (MO₂ ^(n)) to formcrystal framework structures with AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxideunits wherein "M" represents at least one element capable of formingtetrahedral units "MO₂ ^(n) " where "n" is -3, -2, -1, 0 or +1 and is atleast one element selected from the group consisting of arsenic,beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium,magnesium, manganese, titanium and zinc.

The ELAPO molecular sieves have crystalline three-dimensionalmicroporous framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 ;

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "M" represents at least one element capable of formingframework tetrahedral oxides where "M" is at least one element selectedfrom the group consisting of arsenic, beryllium, boron, cobalt,chromium, gallium, germanium, iron, lithium, magnesium, manganese,titanium and zinc.

The relative amounts of element(s) "M", aluminum and phosphorus areexpressed by the empirical chemical formula (anhydrous):

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

where "x", "y" and "z" represent the mole fractions of said "M",aluminum and phosphorus. The individual mole fractions of each "M" (orwhen M denotes two or more elements, M₁, M₂, M₃, etc.) may berepresented by "x₁ ", "x₂ ", "x₃ ", etc. wherein "x₁ ", and "x₂ ", and"x₃ " etc. represent the individual mole fractions of elements M₁, M₂,M₃, and etc. for "M" as above defined. The values of "x₁ ", "x₂ ", "x₃", etc. are as defined for "x", hereinafter, where "x₁ "+"x₂ "+"x₃ " . .. ="x" and where x₁, x₂, x₃, etc. are each at least 0.01.

The ELAPO molecular sieves have crystalline three-dimensionalmicroporous framework structures of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents a molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "M" represents at least one different element (other than Alor P) capable of forming framework tetrahedral oxides, as hereinbeforedefined, and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorus, respectively, present as tetrahedral oxides; ingeneral, said mole fractions "x", "y" and "z" are within the followingvalues for "x", "y" and "z", although as will appear hereinbelow, thelimits for "x", "y" and "z" may vary slightly with the nature of theelement "M":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.02           0.60   0.38                                           B        0.02           0.38   0.60                                           C        0.39           0.01   0.60                                           D        0.98           0.01   0.01                                           E        0.39           0.60   0.01                                           ______________________________________                                    

Also, in general, in a preferred sub-class of the ELAPOs of thisinvention, the values of "x", "y" and "z" in the formula above arewithin the following values for "x", "y" and "z", although again therelevant limits may vary somewhat with the nature of the element "M", asset forth hereinbelow:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.02           0.60   0.38                                           b        0.02           0.38   0.60                                           c        0.39           0.01   0.60                                           d        0.60           0.01   0.39                                           e        0.60           0.39   0.01                                           f        0.39           0.60   0.01                                           ______________________________________                                    

ELAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe elements "M", aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C., until crystals of the ELAPO product areobtained, usually a period of from several hours to several weeks.Typical crystallization times are from about 2 hours to about 30 dayswith from about 2 hours to about 20 days being generally employed toobtain crystals of the ELAPO products. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the ELAPO compositions of the instant invention, it isin general preferred to employ a reaction mixture composition expressedin terms of the molar ratios as follows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; "M" represents at least one element, as abovedescribed, capable of forming tetrahedral oxide framework units, MO₂^(n), with AlO₂ ⁻ and PO₂ ⁺ tetrahedral units; "n " has a value of -3,-2, -1, 0 or +1; and "x", "y" and "z" represent the mole fractions of"M", aluminum and phosphorus, respectively; "y" and "z" each have avalue of at least 0.01 and "x" has a value of at least 0.01 with eachelement "M" having a mole fraction of at least 0.01. In general, themole fractions "x", "y" and "z" are preferably within the followingvalues for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        F        0.01           0.60   0.39                                           G        0.01           0.39   0.60                                           H        0.39           0.01   0.60                                           I        0.98           0.01   0.01                                           J        0.39           0.60   0.01                                           ______________________________________                                    

Further guidance concerning the preferred reaction mixtures for formingELAPOs with various elements "M" will be given below.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (M+Al+P)=(x+y+z)=1.00 mole,whereas in other cases the reaction mixtures are expressed in terms ofmolar oxide ratios and may be normalized to 1.00 mole of P₂ O₅ and/orAl₂ O₃. This latter form is readily converted to the former form byroutine calculations by dividing the total number of moles of "M",aluminum and phosphorus into the moles of each of "M", aluminum andphosphorus. The moles of template and water are similarly normalized bydividing by the total moles of "M", aluminum and phosphorus.

In forming the reaction mixture from which the instant molecular sievesare formed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, preferably nitrogen or phosphorus and mostpreferably nitrogen, which compounds also contain at least one alkyl oraryl group having from 1 to 8 carbon atoms. Particularly preferredcompounds for use as templating agents are the amines, quaternaryphosphonium compounds and quaternary ammonium compounds, the latter twobeing represented generally by the formula R₄ X⁺ wherein "X" is nitrogenor phosphorus and eachd R is an alkyl or aryl group containing from 1 to8 carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 are also suitablyemployed. The mono-, di- and tri-amines are advantageously utilized,either alone or in combination with a quaternary ammonium compound orother templating compound. Mixtures of two or more templating agents caneither produce mixtures of the desired ELAPOs or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; tetrapentylammonium ion; di-n-propylamine;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine;1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Notevery templating agent will direct the formation of every species ofELAPO, i.e., a single templating agent can, with proper manipulation ofthe reaction conditions, direct the formation of several ELAPOcompositions, and a given ELAPO composition can be produced usingseveral different templating agents. The phosphorus source is preferablyphosphoric acid, but organic phosphates such as triethyl phosphate maybe satisfactory, and so also may crystalline or amorphousaluminophosphates such as the AlPO₄ composition of U.S. Pat. No.4,310,440. Organophosphorus compounds, such as tetrabutylphosphoniumbromide, do not apparently serve as reactive sources of phosphorus, butthese compounds may function as templating agents. Conventionalphosphorus salts such as sodium metaphosphate, may be used, at least inpart, as the phosphorus source, but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isopropoxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The element(s) "M" can be introduced into the reaction system in anyform which permits the formation in situ of reactive form of theelement, i.e., reactive to form the framework tetrahedral oxide unit ofthe element. The organic and inorganic salts, of "M" such as oxides,alkoxides, hydroxides, halides and carboxylates, may be employedincluding the chlorides, bromides, iodides, nitrates, sulfates,phosphates, acetates, formates, and alkoxides, including ethoxides,propoxides and the like. Specific preferred reagents for introducingvarious elements "M" are discussed hereinbelow.

While not essential to the synthesis of ELAPO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the ELAPO species to beproduced or a topologically similar species, such as aluminophosphate,alumino-silicate or molecular sieve compositions, facilitates thecrystallization procedure.

After crystallization the ELAPO product may be isolated andadvantageously washed with water and dried in air. The as-synthesizedELAPO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety is present, at least in part, as a charge-balancingcation as is generally the case with as-synthesized aluminosilicatezeolites prepared from organic-containing reaction systems. It ispossible, however, that some or all of the organic moiety is an occludedmolecular species in a particular ELAPO species. As a general rule thetemplating agent, and hence the occluded organic species, is too largeto move freely through the pore system of the ELAPO product and must beremoved by calcining the ELAPO at temperatures of 200° C. to 700° C. tothermally degrade the organic species. In a few instances the pores ofthe ELAPO product are sufficiently large to permit transport of thetemplating agent, particularly if the latter is a small molecule, andaccordingly complete or partial removal thereof can be accomplished byconventional desorption procedures such as carried out in the case ofzeolites. It will be understood that the term "as-synthesized" as usedherein does not include the condition of the ELAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of element "M", aluminum or phosphorus, thecorresponding alcohol is necessarily present in the reaction mixturesince it is a hydrolysis product of the alkoxide. It has not beendetermined whether this alcohol participates in the synthesis process asa templating agent. For the purposes of this application, however, thisalcohol is arbitrarily omitted from the class of templating agents, evenif it is present in the as-synthesized ELAPO material.

Since the present ELAPO compositions are formed from MO₂ ^(n), AlO₂ ⁻and PO₂ ⁺ tetrahedral oxide units which, respectively, have a net chargeof "n", (where "m" may be -3, -2, -1, 0 or +1), -1 and +1, the matter ofcation exchangeability is considerably more complicated than in the caseof zeolitic molecular sieves in which, ideally, there is astoichiometric relationship between AlO₂ ⁻ tetrahedra andcharge-balancing cations. In the instant compositions, an AlO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, aproton (H⁺), a cation of "M" present in the reaction mixture, or anorganic cation derived from the templating agent. Similarly an MO₂ ^(n)tetrahedron, where "n" is negative, can be balanced electrically byassociation with PO₂ ⁺ tetrahedra, a cation of "M" present in thereaction mixture, organic cations derived from the templating agent, asimple cation such as an alkali metal cation, or other divalent orpolyvalent metal cation, a proton (H⁺), or anions or cations introducedfrom an extraneous source. It has also been postulated that non-adjacentAlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH⁻respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS,Washington, DC (1971)].

AsAPO MOLECULAR SIEVES

The AsAPO molecular sieves of U.S. Ser. No. 600,166, filed Apr. 13,1984, and U.S. Ser. No. 830,889 filed Feb. 19, 1986 have a frameworkstructure of AsO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units (where "n" is-1 or +1) and have an empirical chemical composition on an anhydrousbasis expressed by the formula:

    mR:(As.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (As_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements arsenic, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.39           0.01   0.60                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

There are two preferred subclasses of the AsAPO molecular sieves,depending upon whether the value of "n" is -1 or +1 (i.e. whether thearsenic is trivalent or pentavalent), it being understood that mixturesof such are permitted in a given AsAPO. When "n" is -1, the preferredvalues of x, y and z are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.59   0.40                                           b        0.01           0.39   0.60                                           c        0.39           0.01   0.60                                           d        0.59           0.01   0.40                                           ______________________________________                                    

When "n" is +1, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        e        0.01           0.60   0.39                                           f        0.01           0.40   0.59                                           g        0.59           0.40   0.01                                           h        0.39           0.60   0.01                                           ______________________________________                                    

In an especially preferred subclass of the AsAPO molecular sieves inwhich "n"=+1, the values of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        i        0.03           0.52   0.45                                           j        0.03           0.45   0.52                                           k        0.08           0.40   0.52                                           l        0.33           0.40   0.27                                           m        0.33           0.41   0.26                                           n        0.22           0.52   0.26                                           ______________________________________                                    

AsAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofarsenic, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the AsAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 12hours to about 7 days, have been observed. The product is recovered byany convenient method such as centrifugation or filtration.

In synthesizing the AsAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(As.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "x", "y" and "z"represent the mole fractions of arsenic, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.39   0.60                                           I        0.39           0.01   0.60                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those wherein the molefractions "x", "y" and "z" are within the limiting compositional valuesor points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.20           0.55   0.25                                           b        0.20           0.50   0.30                                           c        0.30           0.40   0.30                                           d        0.40           0.40   0.20                                           e        0.40           0.50   0.10                                           f        0.35           0.55   0.10                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing arsenic, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

AsAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare AsAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) As₂ O₅, arsenic(V) oxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

AsAPOs may be prepared by forming a starting reaction mixture bydissolving the arsenic(V) oxide and the H₃ PO₄ in at least part of thewater. To this solution the aluminum oxide or isopropoxide is added.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent and the resulting mixture blendeduntil a homogeneous mixture is observed. The mixture is then placed in alined (polytetrafluoroethylene) stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C.) for a time or placed inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

BAPO MOLECULAR SIEVES

The BAPO molecular sieves of U.S. Ser. No. 599,812, filed Apr. 13, 1984,U.S. Ser. No. 804,248, filed Dec. 4, 1985, and U.S. Ser. No. 29,540,filed Mar. 24, 1987, have a framework structure of BO₂ ⁻, AlO₂ ⁻ and PO₂⁺ tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(B.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (B_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, "x", "y" and "z" represent the mole fractions of the elementsboron, aluminum and phosphorus, respectively, present as tetrahedraloxides. The mole fractions "x", "y" and "z" are generally defined asbeing within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.39           0.01   0.60                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the BAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.59   0.40                                           b        0.01           0.39   0.60                                           c        0.39           0.01   0.60                                           d        0.59           0.01   0.40                                           ______________________________________                                    

An especially preferred subclass of the BAPO molecular sieves are thosein which the mole fraction, "x", of boron is not greater than about 0.3.

BAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofboron, aluminum and phosphorus, preferably an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and/or optionally an alkali or other metal.The reaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the BAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 14 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the BAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(B.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and is an effective amount preferably within therange of greater than zero (0) to about 6, and most preferably not morethan about 1.0; "b" has a value of from zero (0) to about 500,preferably between about 2 and about 300, desirably not greater thanabout 20, and most desirably not greater than about 10; and "x", "y" and"z" represent the mole fractions of boron, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.39   0.60                                           I        0.39           0.01   0.60                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.5 to2.0 moles of B₂ O₃ and from 0.75 to 1.25 moles of Al₂ O₃ for each moleof P₂ O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

The exact nature of the BAPO molecular sieves is not entirely understoodat present, although all are believed to contain BO₂, AlO₂ and PO₂tetrahedra in the three-dimensional microporous framework structure. Thelow level of boron present in some of the instant molecular sieves makesit difficult to ascertain the exact nature of the interactions amongboron, aluminum and phosphorus. As a result, although it is believedthat BO₂ tetrahedra are present in the three-dimensional microporousframework structure, it is appropriate to characterize certain BAPOcompositions in terms of the molar ratios of oxides.

Molecular sieves containing beryllium, aluminum and phosphorus asframework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

BAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) boric acid or trimethylborate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

In the preferred method of synthesizing the BAPO compositions, one firstcombines sources of boron, aluminum and phosphorus to form an amorphousmaterial containing all three elements, and thereafter heats theamorphous material to produce a crystalline BAPO molecular sieve. It isnot necessary that the total quantities of the reactive sources ofboron, aluminum and phosphorus to be used in the final reaction mixturebe present in the amorphous material, since additional quantities of theelements can be added during the later heat treatment; in particular, ithas been found convenient to add additional quantities of phosphorus tothe amorphous material before the heat treatment. The preliminaryformation of the amorphous material assists in the incorporation of theboron into the final molecular sieve.

For example, BAPOs may be prepared by forming a solution of boric acidin a methanolic solution of the templating agent, then adding a hydratedaluminophosphate and water and stirring to form a homogeneous reactionslurry. This slurry is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

BeAPO MOLECULAR SIEVES

The BeAPO molecular sieves of U.S. Ser. No. 599,776, filed Apr. 13,1984, and U.S. Ser. No. 835,293 filed Mar. 3, 1986 have a frameworkstructure of BeO₂ ⁻², AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Be.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Be_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements beryllium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.39           0.01   0.60                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the BeAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.60   0.39                                           b        0.01           0.39   0.60                                           c        0.35           0.05   0.60                                           d        0.35           0.60   0.05                                           ______________________________________                                    

In an especially preferred subclass of the BeAPO molecular sieves thevalues of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        e        0.02           0.46   0.52                                           f        0.10           0.38   0.52                                           g        0.10           0.46   0.44                                           ______________________________________                                    

BeAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofberyllium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the BeAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 14 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the BeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Be.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 50; and "x", "y" and "z"represent the mole fractions of beryllium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.39   0.60                                           I        0.39           0.01   0.60                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those wherein the molefractions "x", "y" and "z" are within the limiting compositional valuesor points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        g        0.04           0.46   0.50                                           h        0.16           0.34   0.50                                           i        0.17           0.34   0.49                                           j        0.17           0.43   0.40                                           k        0.14           0.46   0.40                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing beryllium, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

BeAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BeAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) beryllium sulfate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammoium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

BeAPOs may be prepared by forming a starting reaction mixture bydissolving the beryllium sulfate and the H₃ PO₄ in at least part of thewater. To this solution the aluminum oxide or isopropoxide is added.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent and the resulting mixture blendeduntil a homogeneous mixture is observed. The mixture is then placed in alined (polytetrafluoroethylene) stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C.) for a time or place inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

CAPO MOLECULAR SIEVES

The CAPO molecular sieves of U.S. Ser. No. 599,813, filed Apr. 13, 1984,and U.S. Ser. No. 830,756 filed Feb. 19, 1986 have a framework structureof CrO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units (where "n" is -1, 0 or+1) and have an empirical chemical composition on an anhydrous basisexpressed by the formula:

    mR:(Cr.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Cr_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements chromium, aluminum andphosphorus, respectively, present as tetrahedral oxides. When "n" is -1or +1, the mole fractions "x", "y" and "z" are generally defined asbeing within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.39           0.01   0.60                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

When "n" is 0, the mole fractions "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.47   0.52                                           I        0.94           0.01   0.05                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

There are three preferred subclasses of the CAPO molecular sieves,depending upon whether the value of "n" is -1, 0 or +1 (i.e. whether thechromium has an oxidation number of 3, 4 or 5), it being understood thatmixtures of such are permitted in a given CAPO. When "n" is -1, thepreferred values of x, y and z are within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.59   0.40                                            b        0.01          0.39   0.60                                            c        0.39          0.01   0.60                                            d        0.59          0.01   0.40                                            ______________________________________                                    

In an especially preferred subclass of these CAPSO molecular sieves inwhich "n"=-1, the values of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        n        0.01          0.52   0.47                                            o        0.01          0.42   0.57                                            p        0.03          0.40   0.57                                            q        0.07          0.40   0.53                                            r        0.07          0.47   0.46                                            s        0.02          0.52   0.46                                            ______________________________________                                    

When "n" is 0, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y        z                                              ______________________________________                                        e        0.01         0.60     0.39                                           f        0.01         0.47     0.52                                           g        0.50         0.225    0.275                                          h        0.50         0.40     0.10                                           i        0.30         0.60     0.10                                           ______________________________________                                    

When "n" is +1, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        j        0.01          0.60   0.39                                            k        0.01          0.40   0.59                                            l        0.59          0.40   0.01                                            m        0.39          0.60   0.10                                            ______________________________________                                    

Since the exact nature of the CAPO molecular sieves is not clearlyunderstood at present, although all are believed to contain CrO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the CAPO molecular sievesby means of their chemical composition. This is due to the low level ofchromium present in certain of the CAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between chromium, aluminum and phosphorus. As a result,although it is believed that CrO₂ tetrahedra are substitutedisomorphously for AlO₂ or PO₂ tetrahedra, it is appropriate tocharacterize certain CAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

CAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofchromium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the CAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the CAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Cr.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.6; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "x", "y" and "z"represent the mole fractions of chromium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        L        0.01           0.60   0.39                                           M        0.01           0.39   0.60                                           N        0.39           0.01   0.60                                           O        0.98           0.01   0.01                                           P        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.1 to about 0.4 moles of chromium, and from about 0.75 to about 1.25moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing chromium, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

CAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare CAPOs include:

(a) aluminum isopropoxide, or aluminum chlorhydrol;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) chromium(III) orthophosphate, chromium(III) acetate and chromiumacetate hydroxide, (Cr₃ (OH)₂ (CH₃ COO)₇);

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

CAPOs may be prepared by forming a starting reaction mixture by addingaluminum chlorhydrol or aluminum oxide to a solution of chromium acetatehydroxide in water, then adding successively phosphoric acid and thetemplating agent. Between each addition, and after formation of thefinal mixture, the mixture is blended until a homogeneous mixture isobserved.

Alternatively, the phosphoric acid may be mixed with at least part ofthe water, and aluminum oxide or isopropoxide mixed in. A solution ofchromium acetate hydroxide is then added, followed by the templatingagent, and the resultant mixture mixed until homogeneous.

In a third procedure, amorphous chromium phosphate is ground dry withaluminum oxide and the resultant dry mixture added to an aqueoussolution of phosphoric acid in an ice bath. The templating agent is thenadded, and the final mixture mixed until homogeneous.

Whichever technique is employed to produce the reaction mixture, thismixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

GaAPO MOLECULAR SIEVES

The GaAPO molecular sieves of U.S. Ser. No. 599,771, filed Apr. 13,1984, and U.S. Ser. No. 830,890 filed Feb. 19, 1986 have a frameworkstructure of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements gallium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.34   0.65                                            C        0.34          0.01   0.65                                            D        0.60          0.01   0.39                                            E        0.60          0.39   0.01                                            F        0.39          0.60   0.01                                            ______________________________________                                    

In general, the value of "z" is the GaAPO molecular sieves is notgreater than about 0.60.

In a preferred subclass of the GaAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.59   0.40                                            b        0.01          0.34   0.65                                            c        0.34          0.01   0.65                                            d        0.59          0.01   0.40                                            ______________________________________                                    

In an especially preferred subclass of the GaAPO molecular sieves thevalues of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        e        0.03          0.52   0.45                                            f        0.03          0.33   0.64                                            g        0.16          0.20   0.64                                            h        0.25          0.20   0.55                                            i        0.25          0.33   0.42                                            j        0.06          0.52   0.42                                            ______________________________________                                    

GaAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgallium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali of othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C., until crystals of the GaAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing a the GaAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent, "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably between about 2 and about 20; and "x", "y" and "z"represent the mole fractions of gallium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        G        0.01          0.60   0.39                                            H        0.01          0.39   0.60                                            I        0.39          0.01   0.60                                            J        0.98          0.01   0.01                                            K        0.39          0.60   0.01                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.2 to0.5 mole of Ga₂ O₃ and from 0.3 to 1 mole of Al₂ O₃ for each mole of P₂O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing gallium, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

GaAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GaAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) gallium sulfate or gallium(III) hydroxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-porpylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

GaAPOs may be prepared by forming a starting reaction mixture by mixingthe phosphoric acid with at least part of the water. To this solutionthe aluminum oxide or isopropoxide is added. This mixture is thenblended until a homogeneous mixture is observed. To this mixture thegallium sulfate or gallium hydroxide and the templating agent aresuccessively added and the resulting mixture blended until a homogeneousmixture is observed.

Alternatively, the aluminum oxide may be mixed with a solution of thegallium sulfate or hydroxide, and then the phosphoric acid and thetemplating agent successively added. The resulting mixture is thenblended until a homogeneous mixture is observed.

In a third process, the templating agent may be dissolved in water, thegallium hydroxide or sulfate added with stirring, a solution of thephosphoric acid added, and finally the aluminum oxide mixed in. Theresulting mixture is then blended until a homogeneous mixture isobserved.

Whichever technique is employed to form the reaction mixture, themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

GeAPO MOLECULAR SIEVES

The GeAPO molecular sieves of U.S. Ser. No. 599,807, filed Apr. 13,1984, and U.S. Ser. No. 841,753 filed Mar. 20, 1986 have a frameworkstructure of GeO₂, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Ge.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ge_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.2; and "x", "y" and "z"represent the mole fractions of the elements germanium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.47   0.52                                            C        0.94          0.01   0.05                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the GeAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y       z                                               ______________________________________                                        a        0.01         0.60    0.39                                            b        0.01         0.47    0.52                                            c        0.50         0.225   0.275                                           d        0.50         0.40    0.10                                            e        0.30         0.60    0.10                                            ______________________________________                                    

An especially preferred subclass of the GeAPO molecular sieves are thosein which the value of "x" is not greater than about 0.13.

GaAPO compositions are generally synthesized by hyydrothermalcrystallization from a reaction mixture containing reactive sources ofgermanium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C., until crystals of the GeAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the GeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Ge.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.6; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably between about 10 and about 60; and "x", "y" and "z"represent the mole fractions of germanium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        F        0.01          0.60   0.39                                            G        0.01          0.39   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0.39          0.60   0.01                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.2 to0.4 mole of GeO₂ and from 0.75 to 1.25 mole of Al₂ O₃ for each mole ofP₂ O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing germanium, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

GeAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GeAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) germanium tetrachloride, germanium ethoxide and germanium dioxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

In some cases, it may be advantageous, when synthesizing the GeAPOcompositions, to first combine sources of germanium and aluminum, toform a mixed germanium/aluminum compound (this compound being typicallya mixed oxide) and thereafter to combine this mixed compound with asource of phosphorus to form the final GeAPO composition. Such mixedoxides may be prepared for example by hydrolyzing aqueous solutionscontaining germanium tetrachloride and aluminum chlorhydrol, or aluminumtri-sec-butoxide.

GeAPOs may be prepared by forming a starting reaction mixture by mixingthe phosphoric acid with at least part of the water. To this solution isadded the mixed germanium/aluminum oxide prepared as described above.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent is added and the resulting mixtureblended until a homogeneous mixture is observed.

Alternatively, to a solution of aluminum isopropoxide may be addedgermanium ethoxide. The resultant solution may optionally be dried toproduce a mixed oxide. To the mixed solution or dried oxide are addedsuccessively the phosphoric acid and the templating agent. The resultingmixture is then blended until a homogeneous mixture is observed.

In a third process, a solution is formed by dissolving the phosphorusacid in water, adding aluminum oxide or isopropoxide and mixingthoroughly. To the resultant mixture is added a solution containing thetemplating agent and germanium dioxide. The resulting mixture is thenblended until a homogeneous mixture is observed.

Whichever technique is employed to form the reaction mixture, themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (50° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

LiAPO MOLECULAR SIEVES

The LiAPO molecular sieves of U.S. Ser. No. 599,811, filed Apr. 13,1984, and U.S. Ser. No. 834,921 filed Feb. 28, 1986 have a frameworkstructure of LiO₂ ⁻³, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical composition on an anhydrous basis expressed by the formula:

    mR:(Li.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements lithium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.39          0.01   0.60                                            D        0.60          0.01   0.39                                            E        0.60          0.39   0.01                                            F        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the LiAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.60   0.39                                            b        0.01          0.39   0.60                                            c        0.35          0.05   0.60                                            d        0.35          0.60   0.05                                            ______________________________________                                    

In an especially preferred subclass of the LiAPO molecular sieves thevalues of x, y and z are within the following limits:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        e        0.01          0.52   0.47                                            f        0.01          0.47   0.52                                            g        0.03          0.45   0.52                                            h        0.10          0.45   0.45                                            i        0.10          0.49   0.41                                            j        0.07          0.52   0.41                                            ______________________________________                                    

LiAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources oflithium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the LiAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the LiAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Li.sub.x Al.sub.y O.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 2; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 40; and "x", "y" and "z"represent the mole fractions of lithium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        G        0.01          0.60   0.39                                            H        0.01          0.39   0.60                                            I        0.39          0.01   0.60                                            J        0.98          0.01   0.01                                            K        0.39          0.60   0.01                                            ______________________________________                                    

In an especially preferred subclass of the reaction mixtures, the valuesof "x", "y" and "z" are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        l        0.03          0.50   0.47                                            m        0.03          0.45   0.52                                            n        0.08          0.40   0.52                                            o        0.10          0.40   0.50                                            q        0.04          0.50   0.46                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Since the exact nature of the LiAPO molecular sieves is not clearlyunderstood at present, although all are believed to contain LiO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the LiAPO molecular sievesby means of their chemical composition. This is due to the low level oflithium present in certain of the LiAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between lithium, aluminum and phosphorus. As a result,although it is believed that LiO₂ tetrahedra are substitutedisomorphously for AlO₂ or PO₂ tetrahedra, it is appropriate tocharacterize certain LiAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

Molecular sieves containing lithium, aluminum and phosphorus asframework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

LiAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare LiAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) lithium sulfate or lithium orthophosphate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(1) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

LiAPOs may be prepared by forming a starting reaction mixture bysuspending aluminum oxide in at least part of the water. To this mixturethe templating agent is added. The resultant mixture is then blendeduntil a homogeneous mixture is observed. To this mixture the lithiumphosphate or sulfate is added and the resulting mixture blended until ahomogeneous mixture is observed. Alternatively, an initial mixture maybe formed by mixing aluminum oxide and lithium phosphate or sulfate. Tothe resultant mixture are added successively phosphoric acid and anaqueous solution of the templating agent, and the resulting mixtureblended until a homogeneous mixture is observed.

In a third procedure, the phosphoric acid is mixed with at least part ofthe water, and the aluminum oxide is mixed in. To the resultant mixtureare added lithium sulfate and the templating agent, and the resultingmixture blended until a homogeneous mixture is observed.

Whichever procedure is adopted to form the reaction mixture, the mixtureis then placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) for atime or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

FeTiAPO MOLECULAR SIEVES

The FeTiAPO molecular sieves of U.S. Ser. No. 599,824, filed Apr. 13,1984, and U.S. Ser. No. 902,129 filed Sept. 2, 1986 havethree-dimensional microporous framework structures of FeO₂, TiO₂, AlO₂and PO₂ tetrahedral oxide units having an empirical chemical compositionon an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents iron and titanium; "m"represents the molar amount of "R" present per mole of (M_(x) Al_(y)P_(z))O₂ and has a value of zero (0) to about 0.3; and "x", "y" and "z"represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides. The mole fractions "x", "y"and "z" are generally defined as being within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the FeTiAPO molecular sieves the values of x,y and z are within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

FeTiAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofiron, titanium, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theFeTiAPO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the FeTiAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "x", "y" and "z" represent the molefractions of "M" (iron and titanium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        F        0.02          0.60   0.38                                            G        0.02          0.38   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0.39          0.60   0.01                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Molecular sieves containing iron, titanium, aluminum and phosphorus asframework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

FeTiAPO compositions may be prepared by using numerous reagents. Thepreferred sources of iron and titanium for preparing FeTiAPOs are thesame as those for preparing the FeAPOs and TiAPOs already describedabove. Other reagents which may be employed to prepare FeTIAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphorus acid;

(d) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(j) C-hex: cyclohexylamine;

(k) TMAOH: tetramethylammonium hydroxide;

(l) TPAOH: tetrapropylammonium hydroxide; and

(m) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

FeTiAPOs may be prepared by forming a homogeneous reaction mixturecontaining reactive sources of iron, titanium, aluminum and phosphorus.The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

XAPO MOLECULAR SIEVES

The XAPO molecular sieves of U.S. Ser. No. 599,810, filed Apr. 13, 1984,and U.S. Ser. No. 902,020 filed Sept. 2, 1986 have a three-dimensionalmicroporous framework structures of MO₂ ^(n), AlO₂ and PO₂ tetrahedraloxide units having an empirical chemical composition on an anhydrousbasis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents at least one elementfrom each of the classes of: (1) iron and titanium; and (2) cobalt,magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents amolar amount of "R" present per mole of (M_(x) Al_(y) P_(z))O₂ and has avalue of zero (0) to about 0.3; and "x", "y" and "z" represent the molefractions of "M", aluminum and phosphorus, respectively, present astetrahedral oxides. The mole fractions "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the XAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             x      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

XAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources of"M", aluminum and phosphorus, preferably an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and/or optionally an alkali or other metal.The reaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the XAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the XAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "M" represents at least one element from each of the classesof: (1) iron and titanium; and (2) cobalt, magnesium, manganese andzinc; "b" has a value of from zero (0) to about 500, preferably betweenabout 2 and about 300; and "x", "y" and "z" represent the mole fractionsof "M" (iron and/or titanium, and at least one of cobalt, magnesium,manganese and zinc), aluminum and phosphorus, respectively, and each hasa value of at least 0.01, with the proviso that "x" has a value of atleast 0.02.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        F        0.02          0.60   0.38                                            G        0.02          0.38   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0.39          0.60   0.01                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

XAPO molecular sieves are prepared as follows:

PREPARATIVE REAGENTS

XAPO compositions may be prepared by using numerous reagents. Thepreferred sources of elements "M" for preparing XAPOs are the same asthose for preparing other APOs containing the same elements, asdescribed above and below. Other reagents which may be employed toprepare XAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(j) C-hex: cyclohexylamine;

(k) TMAOH: tetramethylammonium hydroxide;

(l) TPAOH: tetrapropylammonium hydroxide; and

(m) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

XAPOs may be prepared by forming a homogeneous reaction mixturecontaining reactive sources of elements "M", aluminum and phosphorus.The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

MIXED-ELEMENT APO MOLECULAR SIEVES

The mixed element APO molecular sieves of U.S. Ser. No. 599,978, filedApr. 13, 1984, and U.S. Ser. No. 846,088 filed Mar. 31, 1986 have aframework structure of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units,wherein MO₂ ^(n) represents at least two different elements present astetrahedral units "MO₂ ^(n) " with charge "n", where "n" may be -3, -2,-1, 0 or +1. One of the elements "M" is selected from the groupconsisting of arsenic, beryllium, boron, chromium, gallium, germanium,lithium and vanadium, while a second one of the elements "M" is selectedfrom the group consisting of cobalt, iron, magnesium, manganese,titanium and zinc. Preferably, "M" is a mixture of lithium andmagnesium. The mixed-element molecular sieves have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least on organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements "M" (i.e. "x" is the totalof the mole fractions of the two or more elements "M"), aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the mixed-element APO molecular sieves thevalues of x, y and z are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

An especially preferred subclass of the mixed-element APO molecularsieves are those in which the value of x is not greater than about 0.10.

A second group (FCAPO's) of mixed element APO molecular sieves describedin U.S. Ser. No. 600,171, filed Apr. 13, 1984 (not U.S. Pat. No.4,686,093 issued Aug. 11, 1987), have a framework structure of MO₂ ^(n),AlO₂ ⁻ and PO₂ ⁺ tetrahedral units, wherein MO₂ ^(n) represents at leasttwo different elements which are present as tetrahedral units "MO₂ ^(n)" with charge "n", where "n" may be -3, -2, -1, 0 or +1 and which areselected from the group consisting of arsenic, beryllium, boron,chromium, gallium, germanium, lithium and vanadium. These mixed-elementmolecular sieves have an empirical chemical composition on an anhydrousbasis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; and "x", "y" and "z" represent the mole fractions of theelements "M" (i.e. "x" is the total of the mole fractions of the two ormore elements "M"), aluminum and phosphorus, respectively, present astetrahedral oxides. The mole fractions "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of these mixed-element APO molecular sieves thevalues of x, y and z are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

The mixed-element APO compositions are generally synthesized byhydrothermal crystallization from a reaction mixture containing reactivesources of the elements "M", aluminum and phosphorus, preferably anorganic templating, i.e., structure-directing, agent, preferably acompound of an element of Group VA of the Periodic Table, and/oroptionally an alkali or other metal. The reaction mixture is generallyplaced in a sealed pressure vessel, preferably lined with an inertplastic material such as polytetrafluoroethylene and heated, preferablyunder autogenous pressure at a temperature between about 50° C. andabout 250° C., and preferably between about 100° C. and about 200° C.until crystals of the APO product are obtained, usually a period of fromseveral hours to several weeks. Typical effective times of from 2 hoursto about 30 days, generally from about 2 hours to about 20 days, andpreferably about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the mixed-element APO compositions, it is preferred toemploy a reaction mixture composition expressed in terms of the molarratios as follows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20, and most desirably not morethan about 10; and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorus, respectively, "y" and "z" each having a valueof at least 0.01 and "x" having a value of at least 0.02, with eachelement "M" having a mole fraction of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                        Point    x             y      z                                               ______________________________________                                        F        0.02          0.60   0.38                                            G        0.02          0.38   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0.39          0.60   0.01                                            ______________________________________                                    

Preferred reaction mixtures are those containing not more than about 0.2moles of the metals "M" per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Since the exact nature of the mixed-element APO molecular sieves is notclearly understood at present, although all are believed to contain MO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the mixed-element APOmolecular sieves by means of their chemical composition. This is due tothe low level of the elements "M" present in certain of themixed-element APO molecular sieves prepared to date which makes itdifficult to ascertain the exact nature of the interaction between themetals "M", aluminum and phosphorus. As a result, although it isbelieved that MO₂ tetrahedra are substituted isomorphously for AlO₂ orPO₂ tetrahedra, it is appropriate to characterize certain mixed-elementAPO compositions by reference to their chemical composition in terms ofthe mole ratios of oxides.

Molecular sieves containing the metals "M", aluminum and phosphorus asframework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

Mixed-element APO compositions may be prepared by using numerousreagents. Reagents which may be employed to prepare mixed-element APOsinclude:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) lithium phosphate or magnesium hydroxide or appropriate salts of theother elements "M", as described above;

(e) TEACH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

Mixed element APOs may be prepared by forming a starting reactionmixture by mixing aluminum oxide, magnesium hydroxide, lithium phosphate(or the corresponding salts of the other elements "M"). To this mixturethe phosphoric acid is added. The resultant mixture is then blendeduntil a homogeneous mixture is observed. To this mixture the templatingagent is added and the resulting mixture blended until a homogeneousmixture is observed.

The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

SILICOALUMINOPHOSPATE MOLECULAR SIEVES

The preferred NZMSs, to date, are the silicoaluminophosphate molecularsieves described in U.S. Pat. No. 4,440,871, and U.S. Ser. No. 575,745,filed Jan. 31, 1984. The use of such catalysts in reforming catalysts oras components in heretofore employed reforming/dehydrocyclizationcatalysts provides improved catalysts and provides productscharacterized by an improved selectivity to iso-products and providesimproved activity in reforming/dehydrocyclization reactions.

The silicoaluminophosphate molecular sieves of U.S. Pat. No. 4,440,871and the aforementioned applications, are disclosed as microporouscrystalline silicoaluminophosphates, the pores of which are uniform andhave nominal diameters of greater than about 3 Angstroms and whoseessential empirical chemical composition in the as-synthesized andanhydrous form is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from 0.02to 0.3; "x", "y" and "z" represent the mole fractions of silicon,aluminum and phosphorus, respectively, present as tetrahedral oxides,said mole fractions being such that they are within the pentagonalcompositional area defined by points A, B, C, D and E of the ternarydiagram of FIG. 5 of the aforementioned U.S. Pat. No. 4,440,871, and arepreferably within the pentagonal compositional area defined by points a,b, c, d and e of FIG. 6 of this patent. The SAPO molecular sieves ofU.S. Pat. No. 4,440,871 are also described as silicoaluminophosphateshaving a three-dimensional microporous framework structure of PO₂ ⁺,AlO₂ ⁻ and SiO₂ tetrahedral units, and whose essential empiricalchemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "x", "y" and "z" represent, respectively,, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the aforementionedpatent, said silicoaluminophosphate having a characteristic X-ray powderdiffraction pattern which contains at least the d-spacings set forthbelow in any one of Tables I, III, V, VII, IX, XIII, XV, XVII, XXI,XXIII or XXV of U.S. Pat. No. 4,440,871. Further, the as-synthesizedcrystalline silicoaluminophosphates of U.S. Pat. No. 4,440,871 may becalcined at a temperature sufficiently high to remove at least some ofany organic templating agent present in the intracrystalline pore systemas a result of such synthesis. The silicoaluminophosphates of U.S. Pat.No. 4,440,871 are generally referred to therein as "SAPO", as a class,or as "SAPO-n" wherein "n" is an integer denoting a particular SAPO asits preparation is reported in U.S. Pat. No. 4,440,871. The preparationof the SAPOs is disclosed in U.S. Pat. No. 4,440,871, incorporatedherein by reference.

Medium pore(MP)-SAPOs include SAPO-11, SAPO-31, SAPO-40 and SAPO-41.

The species SAPO-11 as referred to herein is a silicoaluminophosphatematerial having a three-dimensional microporous crystal frameworkstructures of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units, and whoseessential empirical chemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "x", "y" and "z" represent, respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the patent, andpreferably within the area bounded by points a, b, c, d and e on theternary diagram which is FIG. 6 of the patent, saidsilicoaluminophosphate having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-11                                                                                                       Relative                                      2θ               d(Å) Intensity                                     ______________________________________                                         9.4-9.65              9.41-9.17                                                                              m                                             20.3-20.6              4.37-4.31                                                                              m                                             21.0-21.3              4.23-4.17                                                                              vs                                             21.1-22.35            4.02-3.99                                                                              m                                             22.5-22.9 (doublet)    3.95-3.92                                                                              m                                             23.15-23.35            3.84-3.81                                                                              m-s                                           ______________________________________                                    

The species SAPO-31 as referred to herein is a silicoaluminophosphatehaving a three-dimensional microporous crystal framework structure ofPO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units, and whose essential empiricalchemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "x", "y" and "z" represent, respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the patent, andpreferably within the area bounded by points a, b, c, d and e on theternary diagram which is FIG. 6 of the patent, saidsilicoaluminophosphate having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-31                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        8.5-8.6        10.40-10.28                                                                             m-s                                                  20.2-20.3      4.40-4.37 m                                                    21.9-22.1      4.06-4.02 w-m                                                  22.6-22.7      3.93-3.92 vs                                                   31.7-31.8      2.823-2.814                                                                             w-m                                                  ______________________________________                                    

The species SAPO-40 as referred to herein is a silicoaluminophosphatematerial having a three-dimensional microporous crystal frameworkstructure of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units, and whoseessential empirical chemical composition on an anhydrous basis is

    mR:(Si.sub.x Al.sub.y P.sub.x)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, "x", "y" and "z" represent respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety,, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the patent, orpreferably within the area bounded by points a, b, c, d and e on theternary diagram which is FIG. 6 of the patent, saidsilicoaluminophosphate having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-40                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        7.5-7.7        11.79-11.48                                                                             vw-m                                                 8.0-8.1        11.05-10.94                                                                             s-vs                                                 12.4-12.5      7.14-7.08 w-vs                                                 13.6-13.8      6.51-6.42 m-s                                                  14.0-14.1      6.33-6.28 w-m                                                  27.8-28.0      3.209-3.18                                                                              w-m                                                  ______________________________________                                    

The species SAPO-41 as referred to herein is a silicoaluminophosphatehaving a three-dimensional microporous crystal framework structure ofPO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units, and whose essential empiricalchemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "x", "y" and "z" represent, respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the patent, orpreferably within the area bounded by points a, b, c, d and e on theternary diagram which is FIG. 6 of the patent, saidsilicoaluminophosphate having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-41                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w-m                                                  20.5-20.6      4.33-4.31 w-m                                                  21.1-21.3      4.21-4.17 vs                                                   22.1-22.3      4.02-3.99 m-s                                                  22.8-23.0      3.90-3.86 m                                                    23.1-23.4      3.82-3.80 w-m                                                  25.5-25.9      3.493-3.44                                                                              w-m                                                  ______________________________________                                    

Large pore(LP)-SAPOs include SAPO-5 and SAPO-37.

The species SAPO-5 as referred to herein is a silicoaluminophosphatematerial having a three-dimensional microporous crystal frameworkstructure of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units, and whoseessential empirical chemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, "x", "y" and "z" represent respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 5 of the patent, orpreferably within the area bounded by points a, b, c, d and e on theternary diagram which is FIG. 6 of the patent, saidsilicoaluminophosphate having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-5                                                                                                 Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w-m                                                  7.35-7.65      11.79-11.48                                                                             vw-m                                                  19.6-19.95    11.05-10.94                                                                             s-vs                                                 20.9-21.3      7.14-7.08 w-vs                                                 22.3-22.6      6.51-6.42 m-s                                                  25.85-26.15    3.46-3.40 w-m                                                  27.8-28.0      3.209-3.18                                                                              w-m                                                  ______________________________________                                    

The species SAPO-37 as referred to herein is a silicoaluminophosphatehaving a microporous crystalline framework structure and whose essentialempirical chemical composition in the as-synthesized form and on ananhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" has a value of from 0.02 to 0.3,"x", "y" and "z" represent respectively, the mole fractions of silicon,aluminum and phosphorus present in the oxide moiety, said mole fractionsbeing within the compositional area bounded by points A, B, C, D and Eon the ternary diagram which is FIG. 5 of the patent, or preferablywithin the area bounded by points a, b, c, d and e on the ternarydiagram which is FIG. 6 of the patent, said silicoaluminophosphatehaving a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth below:

    ______________________________________                                        SAPO-37                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w-m                                                  6.1-6.3        14.49-14.03                                                                             vs                                                   15.5-15.7      5.72-5.64 w-m                                                  18.5-18.8      4.80-4.72 w-m                                                  23.5-23.7      3.79-3.75 w-m                                                  26.9-27.1      3.31-3.29 w-m                                                  ______________________________________                                    

NZ-MS CATALYSTS

The NZMSs useful in the present invention have at least three frameworkelements present as tetrahedral oxides, thus producing acidity andcatalytic properties superior to those of zeolites, for example, andthse species are preferred. Thus, the group consisting of the SAPO,ELAPSO, ELAPO, MeAPO, FeAPO and TiAPO molecular sieves is preferred.

The specific NZ-MSs employed in the instant invention are characterizedin their calcined form by an adsorption of oxygen of at least 4 percentby weight at a partial pressure of 100 torr and a temperature of -186°C. Further, the NZ-MSs are preferably characterized in their calcinedform by an adsorption of isobutane of at least 2 percent by weight at apartial pressure of 500 torr and a temperature of 20° C. Thenon-zeolitic molecular sieves are more preferably characterized by bothof the aforementioned adsorption criteria and also characterized by anadsorption of triethylamine of from zero to less than 5 percent byweight, preferably less than 3 weight percent, at a partial pressure of500 torr and a temperature of 20° C.

The NZ-MSs employed herein are characterized by the aforementionedadsorption criteria. Certain NZ-MS species which may be employed hereinare generally designated in one or more of the aforementioned subclassesof the class of NZ-MS by a "-n" designation of -5, -11, -14, -17, -18,-25, -31, -33, -34, -35, -36, -37, -39, -40, -40, -41, -44 and -47.

NZMSs characterized by the above described adsorption of isobutaneinclude, but are not limited to, ELAPSO-5, ELAPSO-11, ELAPSO-31,ELAPSO-36, ELAPSO-37, ELAPSO-40, ELAPSO-41, SAPO-5, SAPO-11, SAPO-31,SAPO-36, SAPO-37, SAPO-40, SAPO-41, CoAPSO-5, CoAPSO-11, CoAPSO-31,CoAPSO-36, CoAPSO-37, CoAPSO-40, CoAPSO-41, FeAPSO-5, FEAPSO-11,FeAPSO-31, FeAPSO-36. FeAPSO-37, FeAPSO-40, FeAPSO-41, MgAPSO-5,MgAPSO-11, MgAPSO-31, MgAPSO-36, MgAPSO-37, MgAPSO-40, MgAPSO-41,MnAPSO-5, MnAPSO-11, MnAPSO-31, MnAPSO-36, MnAPSO-37, MnAPSO-40,MnAPSO-41, TiAPSO-5, TiAPSO-11, TiAPSO-31, TiAPSO-36, TiAPSO-37,TiAPSO-40, TiAPSO-41, ZnAPSO-5, ZnAPSO-11, ZnAPSO-31, ZnAPSO-36,ZnAPSO-37, ZnAPSO-40, ZnAPSO-41, CoMnAPSO-5, CoMnAPSO-11, CoMnAPSO-36,CoMnAPSO-37, CoMnAPSO-40, CoMnAPSO-41, CoMnMgAPSO-5, CoMnMgAPSO-11,CoMnMgAPSO-31, CoMnMgAPSO-36, CoMnMgAPSO-37, CoMnMgAPSO-40,CoMnMgAPSO-41, AsAPSO-5, AsAPSO-11, AsAPSO-31, AsAPSO-36, AsAPSO-37,ASAPSO-40, AsAPSO-41, BAPSO-5, BAPSO-11, BAPSO-31, BAPSO-36, BAPSO-37,BAPSO-40, BAPSO-41, BeAPSO-5, BeAPSO-11, BeAPSO-31, BeAPSO-36,BeAPSO-37, BeAPSO-40, BeAPSO-41, CAPSO-5, CAPSO-11, CAPSO-31, CAPSO-36,CAPSO-37, CAPSO-40, CAPSO-41, GaAPSO-5, GaAPSO-11, GaAPSO-31, GaAPSO-36,GaAPSO-37, GaAPSO-40, GaAPSO-41, GeAPSO-5, GeAPSO-11, GeAPSO-31,GeAPSO-36, GeAPSO-37, GeAPSO-40, GeAPSO-41, LiAPSO-5, LiAPSO-11,LiAPSO-31, LiAPSO-36, LiAPSO-37, LiAPSO-40, LiAPSO-41, MeAPO-5,MeAPO-11, MeAPO-31, MeAPO-36, MeAPO-37, MeAPO-40, MeAPO-41, TiAPO-5,TiAPO-11, TiAPO-31, TiAPO-36, TiAPO-37, TiAPO-40, TiAPO-41, FCAPO-5,FCAPO-11, FCAPO-31, FCAPO-36, FCAPO-37, FCAPO-40, FCAPO-41, AsAPO-5,AsAPO-11, AsAPO-31, AsAPO-36, AsAPO-37, AsAPO-40, AsAPO-41, BAPO-5,BAPO-11, BAPO-31, BAPO-36, BAPO-37, BAPO-40, BAPO-41, BeAPO-5, BeAPO-11,BeAPO-31, BeAPO-36, BeAPO-37, BeAPO-40, BeAPO-41, CAPO-5, CAPO-11,CAPO-31, CAPO-36, CAPO-37, CAPO-40, CAPO-41, GaAPO-5, GaAPO-11,GaAPO-31, GaAPO-36, GaAPO-37, GaAPO-40, GaAPO-41, GeAPO-5, GeAPO-11,GeAPO-31, GeAPO-36, GeAPO-37, GeAPO-40, GeAPO-41, LiAPO-5, LiAPO-11,LiAPO-31, LiAPO-36, LiAPO-37, LiAPO-40, LiAPO-41, and the mixed-elementAPOs which may be designated MAPO-5, MAPO-11, MAPO-31, MAPO-36, MAPO-37,MAPO-40 and MAPO-41, and mixtures thereof.

The above characterization of the NZ-MSs employed in the instantinvention relates to an adsorption characterization that is carried outon a NZ-MS which has been subjected to a post synthesis treatment, e.g.,calcination or chemical treatment, to remove a substantial portion ofthe template "R" which is present as a result of synthesis. Although aparticular NZ-MS is characterized herein by reference to its adsorptionof isobutane or triethylamine in its calcined form, the instantinvention necessarily includes the use of non-calcined or modifiedNZ-MSs which are characterized by such adsorption in the modified orcalcined form, since upon use of such a non-calcined NZ-MS in theinstant process at effective hydrocracking conditions the NZ-MS may becalcined or hydrothermally treated in situ so as to have one or more ofthe characteristic adsorptions of oxygen, isobutane and triethylamine.Thus, the NZ-MS may be rendered in situ to a form characterized by theaforementioned adsorption characteristics and such is within the scopeof the instant invention. For example, an as-synthesized MgAPO-11 orMgAPSO-11 is not characterized by the aforementioned adsorption ofisobutane due to the presence of template "R" which is present as aresult of synthesis, although the calcined forms of MgAPO-11 andMgAPSO-11 are characterized by the aforementioned adsorption ofisobutane. Thus, reference to a NZ-MS having a particular adsorptioncharacteristic in its calcined form is not intended to exclude the useof the NZ-MS in its as-synthesized form which upon in-situ calcination,hydrothermal treatment and/or other treatment, e.t., ion exchange withsuitable atoms, would have such adsorption characteristics.

As discussed above, it has been found that this class of NZ-MS, whenused in combination with hydrocracking catalyst components, providesproduct distributions not observed by use of traditional hydrocrackingcatalysts containing zeolitic aluminosilicate components. Heretofore,the hydrocracking catalysts of the prior art (such as those containingzeolites) have generally exhibited a decrease in gasoline yield and/orconversion in the optimization of a particular process variable orproduct characteristic e.g., octane of the gasoline product. Suchpenalties are reduced or eliminated by use of the processes of thepresent invention. An increase in the isoparaffin to normal paraffinsratio is desirable in gasoline products, since such an increase is anindication of higher octane products.

While not wishing to be bound by theory, it is believed that the NZMScomponent of the catalysts used in the present invention isomerizesnormal paraffins in the light gasoline fraction to isoparaffins withoutcontributing significantly to their conversion by hydrocracking. Thus,these non-zeolitic molecular sieve catalyst additives effect an octaneboost without yield loss or increased conversion of feed. Thetraditional hydrocracking catalyst component of the present invention isbelieved to contribute predominantly to the conversion of feed to thegasoline products. Heretofore, the zeolite-containing hydrocrackingcatalysts of the prior art have required that certain penalties beendured for the optimization of particular process variables or productcharacteristics, e.g., octane number.

In addition to the above improvement in the octane of the gasolineproducts, this improvement in octane can now be achieved by usingselected non-zeolitic molecular sieves in combination with base metalsas hydrogenation components of traditional hydrocracking catalysts. Inthe past, noble metal catalysts were heretofore required to obtain highoctane products. Since base metal catalysts are generally more resistantto feed contaminants such as sulfur-containing organic compounds, theinstant invention provides more contaminant-resistant catalysts withoutthe octane penalty heretofore associated with base metal catalysts. Whennoble metal hydrogenation components are employed with the instantNZ-MS(s) in hydrocracking catalysts, the instant invention furtherprovides an improvement in the isoparaffin content of the gasolineproducts.

The NZ-MSs of the instant invention are employed in conjunction withhydrocracking catalysts, preferably traditional hydrocracking catalystssuch as those containing zeolitic aluminosilicate cracking components.The zeolitic aluminosilicate component of such catalysts may be anyaluminosilicate heretofore employed as a component in hydrocrackingcatalysts. Representative of the zeolitic aluminosilicates disclosedheretofore as employable as component parts of traditional hydrocrackingcatalysts are Zeolite Y (including steam stabilized and ultrastable Y),Zeolite X, Zeolite beta (U.S. Pat. No. 3,308,069), Zeolite KZ-20 (U.S.Pat. No. 3,445,727), Zeolite ZSM-3 (U.S. Pat. No. 3,415,736), faujasite,LZ-10 (U.K. Pat. No. 2,014,970, June 9, 1982), US-Y, ZSM-type zeolites,erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-typezeolities and mixtures thereof. Traditional cracking catalystscontaining amounts of Na₂ O less than about one percent by weight aregenerally preferred.

Representative Y-type zeolites believed employable herein include, butare not limited to, those zeolite Y compositions disclosed in U.S. Pat.Nos.: 3,130,007; 3,835,032; 3,830,725; 3,293,192; 3,449,070; 3,839,539;3,867,310; 3,929,620; 3,929,621; 3,933,983; 4,058,484; 4,085,069;4,175,059; 4,192,778; 3,676,368; 3,595,611; 3,594,331; 3,536,521;3,293,192; 3,966,643; 3,966,882 and 3,957,623.

Another zeolitic aluminosilicate employable herein is "LZ-210",described in E.P.C. Publication No. 82,211 published June 29, 1983, andU.S. Pat. No. 4,503,023, incorporated herein by reference. In oneembodiment the silica-to-alumina mole ratio is between about 7 and about11 and preferably between about 8 and about 10. Hydrocracking catalystscontaining LZ-210 zeolites are disclosed in copending U.S. Ser. No.490,951, filed May 2, 1983, and in U.S. Pat. No. 4,735,928, which issuedfrom a continuation thereof, incorporated herein by reference, and suchmay be employed herein as the optional traditional hydrocrackingcomponent.

The term "ZSM-type" zeolites is generally employed in the art to referto those zeolites denominated by the nomenclature "ZSM-n" where "n" isan integer. The ZSM-type aluminosilicates include but are not limited toZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48; and other similarmaterials having such structures.

ZSM-5 is described in greater detail in U.S. Pat. No. 3,702,886 and Re29,948. The entire descriptions contained within those patents,particularly the X-ray diffraction pattern of therein disclosed ZSM-5,are incorporated herein by reference.

ZSM-11 is described in U.S. Pat. No. 3,709,979. That description, and inparticular the X-ray diffraction pattern of said ZSM-11, is incorporatedherein by reference.

ZSM-12 is described in U.S. Pat. No. 3,832,449. That description, and inparticular the X-ray diffraction pattern disclosed therein, isincorporated herein by reference.

ZSM-23 is described in U.S. Pat. No. 4,076,842. The entire contentthereof, particularly the specification of the X-ray diffraction patternof the disclosed zeolite, is incorporated herein by reference.

ZSM-35 is described in U.S. Pat. No. 4,016,245. The description of thatzeolite, and particularly the X-ray diffraction pattern thereof, isincorporated herein by reference.

ZSM-38 is more particularly described in U.S. Pat. No. 4,046,859. Thedescription of that zeolite, and particularly the specified X-raydiffraction pattern hereof, is incorporated herein by reference.

ZSM-48 is more particularly described in U.S. Pat. No. 4,423,021. Thedescription of that zeolite, and particularly the specified X-raydiffraction pattern thereof, is incorporated herein by reference.

Of the above ZSM-n and ZSM-type zeolites, those having the pentasilstructure are most preferred, such as ZSM-5 and ZSM-11.

In addition, crystalline silicates such as silicalite (U.S. Pat. No.4,061,724) may be employed with the NZ-MSs of the instant invention.

FORMULATION OF NZ-MS HYDROCRACKING CATALYSTS

The catalysts of the instant invention comprise at least one NZ-MS, asabove characterized, and also contain one or more traditionalhydrocracking catalysts, including zeolitic aluminosilicate componentsand hydrogenation components such as nickel, and tungsten sulfide andthe like. The relative amounts of the NZ-MS component and traditionalhydrocracking catalyst component, will depend at least in part, on theselected crude oil feedstock and on the desired product distribution tobe obtained therefrom, but in all instances an effective amount of atleast one NZ-MS is employed. The NZ-MS is preferably present in anamount effective to increase the octane number of the light gasolinewithout substantially decreasing yield or increasing conversion. When azeolitic aluminosilicate is employed as a part of the traditionalhydrocracking component the relative weight ratio of the zeoliticaluminosilicate to the NZ-MS is generally between about 1:10 and about500:1, desirably between about 1:10 and about 200:1, preferably betweenabout 1:2 and about 50:1, and most preferably is between about 1:1 andabout 20:1. The zeolitic aluminosilicate should be present in an amounteffective to convert the feed to lower molecular weight products such asgasoline.

The zeolitic aluminosilicate and NZ-MS may be ion-exchanged with aselected cation(s) and/or thermally treated either before or aftermixture with each other or after such have been added separately orconcurrently to one or more inorganic oxide matrix components. When theNZ-MS molecular sieves are ion exchanged such are preferably exchangedwith a hydrogen-forming cation species, e.g., NH₄ ₊, H⁺, quaternaryammonium cations, etc. The NZ-MS preferably has at least part of itscations as hydrogen-forming cation species.

Any ion-exchange, impregnation and/or occlusion of the NZ-MS and/orzeolitic aluminosilicate(s), if any, may be carried out by contactingsuch with a solution of at least one cation, including those selectedfrom the group of cations consisting of ammonium, Group IIA, Group IIIA,Group IIIB to VIIB and rare earth cations selected from the groupconsisting of cerium, lanthanum, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, lutetium and mixtures thereof. The exact nature ofthe relationship of rare earth cations and the NZ-MSs and their effecton the activity and/or selectivity of the NZ-MS-containing catalyst isnot clearly understood at present. The cation(s), e.g., rare earthcation, may replace at least a portion of the cations initially presentin the zeolitic aluminosilicate and/or NZ-MS or may be present asimpregnated or occluded species. Such cations may be present in aneffective amount which may be between about 0.1 weight percent and about20 weight percent, typically between about 0.5 and about 10 weightpercent, based on the weight of the starting zeolitic aluminosilicateand/or NZ-MS.

The hydrocracking catalysts of this invention contain an effectiveamount of at least one hydrogenation component of the type commonlyemployed in hydrocracking catalysts. The hydrogenation catalyst orcomponent is generally selected from the group of hydrogenationcatalysts consisting of one or more metals of Group VIB and Group VIII,including the salts, complexes and solutions containing such metals. Thehydrogenation catalyst is preferably selected from the group of metals,salts and complexes of the group consisting of platinum, palladium,rhodium, iridium and mixtures thereof or the group consisting of nickel,molybdenum, cobalt, tungsten, chromium and mixtures thereof. Asrecognized in the art, the noble and base metals will not generally beemployed in the same catalyst system although such are not excluded fromthe scope of this invention. Reference to the catalytically active metalor metals is intended to encompass such metal or metals in the elementalstate or in some form such as an oxide, sulfide, halide, carboxylate andthe like.

The hydrogenation component is present in an effective amount to providethe hydrogenation function of the hydrocracking catalyst. When thehydrogenation catalyst is a noble metal it is generally present in anamount between about 0.05 percent and about 1.5 percent by weight basedon the total weight of the hydrocracking catalyst, including the weightof any binder or matrix material which may be present, as hereinafterdiscussed, although effective amounts outside this range may beemployed. Although effective amounts in excess of 1.5 percent by weightmay be employed, the preferred effective amount of the noble metalhydrogenation catalyst is between about 0.3 percent and about 1.2percent by weight. When the hydrogenation catalyst is a base metal(s)the effective amount will generally be between about 1.0 percent andabout 30 percent by weight or more of the base metal, expressed as theoxide(s), based on the total weight of the hydrocracking catalyst,although effective amounts outside this range may be employed.

The final form of the hydrogenation component of the hydrocrackingcatalyst is not narrowly limited herein but may be a metal oxide, metalsulfide or other catalytically active form. Since sulfur is typicallypresent in the hydrocarbon feedstock being treated, the actual form ofsome of the hydrogenation component(s) may well in some cases be atleast in part a sulfide due to in situ reactions. When a noble metal isemployed as the hydrogenation component the catalyst is generallyactivated in air and then reduced in a hydrogen atmosphere. When a basemetal is employed it is usually also treated with a sulfur compound.

The hydrogenation components can be incorporated into the overallcatalyst composition by any one of numerous procedures. They can beadded either to the NZ-MS component, zeolitic aluminosilicate component,if any, or to any metal oxide or to a combination thereof by ionexchange, impregnation, occlusion and the like. In the alternative,multiple hydrogenation components (two or more) may be added as powdersin formulation of the catalyst. They may be added by co-mulling,impregnation, or ion exchange whereby one or more may be added to theNZ-MS and/or zeolitic aluminosilicate. For example, noble or base metalcompounds, such as the sulfides, oxides or water-soluble salts, can beadded by co-mulling, impregnation or precipitation before the compositeis finally calcined. In the alternative these components can be added tothe finished particle by impregnation with an aqueous, alcoholic,hydrocarbon, or other nonaqueous solution of soluble compounds orprecursors. Impregnation or co-mulling are generally the preferredtechniques when the hydrogenation component is a base metal whileion-exchange techniques are generally preferred when noble metals areemployed as the hydrogenation catalyst.

Although the hydrogenation comonents can be combined with the NZ-MS andzeolitic aluminosilicate as the oxides, that is generally not the case.They are usually added as a metal salt which can be thermally convertedto the corresponding oxide in an oxidizing atmosphere or reduced to themetal with hydrogen or other reducing agent. The composition can besulfided by reaction with a sulfur donor such as carbon disulfide,hydrogen sulfide, hydrocarbon thiols, elemental sulfur, and the like,described above. The above oxidizing or sulfiding processes aregenerally carried out on catalyst compositions which have been partiallydried (as desired), tableted, pelleted, extruded (with binder ormatrix), or formed by other means and then calcined, e.g., at atemperature above 600° F., usually above 800° F.

It is well known in the art that hydrocracking catalysts are generallyemployed with a binder material or, as commonly referred to, with aninorganic oxide matrix which can be inert or also catalytically active.For example inorganic matrices such as clay, silica, alumina,silica-alumina, silica-zirconia, silica-magnesia, alumina-boria,alumina-titania and the like and mixtures thereof may be employed. Aninorganic oxide need not always be employed such as in the case of apreform containing the NZ-MS or may be employed in an amount betweenabout 1 percent and about 95 percent by weight, preferably between about10 percent and about 80 percent by weight, based on the total weight ofthe hydrocracking composition.

The term "crude oil feedstock" is used herein to denominate any crudeoil feedstock or portion thereof and includes full range crude oils fromprimary, secondary or tertiary recovery from conventional or offshoreoil fields and to the myriad of feedstocks derived therefrom. "Crude oilfeedstocks" may also be "syncrudes" such as those that can be derivedfrom coal, shale oil, tar sands and bitumens. The crude oil feedstockmay be virgin (straight run) or generated synthetically by blending.Such crude oil feedstocks are traditionally desalted prior to use sincesodium chloride is known to be a poison in many hydrocrackingoperations. Further, the term "crude oil feedstocks" is intended toinclude component parts of crude oils which have heretofore beengenerally employed as feedstocks or potential feeds and includes feedssuch as distillate gas oils, vacuum gas oils, atmospheric and vacuumresidual oils, syncrudes, pulverized coal and fractions boiling abovethe traditional end of the gasoline boiling range which generallyincludes compounds containing greater than about eleven carbon atoms andcombinations thereof. The feedstocks employed in hydrocracking generallyhave boiling points between about 400° F. and about 900° F.

In hydrocracking processes the hydrocarbon feedstock to be charged tothe hydrocracking unit typically boils above 300° f., preferably betweenabout 400° F. and 1200° F. and more preferably between about 400° F. andabout 900° F. The hydrocarbon feed may be derived from many sources, asabove discussed, including: catalytic cracking processes; cokingprocesses; fractionators from crude oil; hydrocracking; pyrolysisprocesses; just to name a few. When operating a hydrocracking process tomaximize gasoline production, the typical feedstock currently incommercial use has an end boiling point not greater than about 800° F.Typically, a light catalytic cycle oil, or a light virgin gas oil, ormixtures thereof, boiling in the range of from about 300° F. to 800° F.is employed as a feedstock. The feed may be pre-treated in ahydrotreater to effect hydrodenitrification and/or hydrodesulfurization.

The feed may have a significant sulfur content, present as hydrogensulfide, ranging from 0.1 to 3 weight percent, and the nitrogen content,present as ammonia, may be present in an amount up to 4000 parts permillion or more. Temperature, space velocity, and other processvariables may be adjusted to compensate for the effects of nitrogen onthe hydrocracking catalyst activity. The feedstock is contacted in thehydrocracking reaction zone with the hydrocracking catalyst in thepresence of hydrogen-containing gas and/or a hydrogen generatingcompound. Hydrogen is consumed in the hydrocracking process and anexcess of hydrogen is typically maintained in the reaction zone.Advantageously, a hydrogen-to-oil (feed) ratio of at least 1,000standard cubic feet of hydrogen per barrel of feed (SCFB) is employed,and the hydrogen-to-oil ratio may range up to 20,000 SCFB, preferably,about 4,000 to 12,000 SCFB is employed. The hydrocracking reaction zoneis typically operated under conditions of elevated temperature andpressure. The total hydrocracking pressure is usually between about 400and about 4,000 pounds per square inch gauge (psig) and, preferably,between about 500 and 2000 psig. The hydrocracking reaction isexothermic and a temperature rise occurs across the catalyst bed.Therefore, the inlet temperature to the hydrocracking reaction zone maybe 10° to 40° F. lower than the exit temperature. The averagehydrocracking catalyst bed temperature is between about 450° F. and 800°F. depending on the presence or absence of NH₃ and the catalyst's age.The liquid hourly space velocity (LHSV) typically is between 0.2 and 5volume of feed per hour per volume of catalyst, and preferably between0.25 and 4 LHSV.

EXAMPLES

The following examples were carried out to demonstrate the use of thehydrocracking catalysts and hydrocracking processes of the instantinvention and are not intended to be limiting thereof.

EXPERIMENTAL PROCEDURE

Hydrocracking catalysts were prepared as described in the followingexamples and tested for their utility as hydrocracking catalysts. Thecatalysts were employed as hydrocracking catalysts in a first stagehydrocracking process.

A selected catalyst was evaluated for hydrocracking by contacting thehydrocarbon feed (gas oil feed boiling between about 332° F. and about853° F. (ASTM test method D-2887) and containing about 5000 ppm sulfurand 2000 ppm nitrogen) with the selected catalyst. The feedstock has adensity of 0.8341 g/cc at 60° F. The sulfur and nitrogen are present byadding 0.5 weight percent sulfur in the form of thiophene and 0.2 weightpercent nitrogen in the form of t-butylamine to the feedstock, whereinthe weight percents were based on the total weight of the feedstock. Thehydrocracking process was carried out at a pressure of about 1450 psigand an temperature between about 685° F. and about 709° F. and at a LHSV(liquid hourly space velocity) of about 1.7. Hydrogen was introduced ata rate of about 8000 standard cubic feet of hydrogen per barrel offeedstock.

The hydrocracking experiments were carried out by introducing a selectedfeedstock to a stainless steel reactor having an axial thermowell. Thetemperature in the reactor was monitored by thermocouple in thethermowell. The catalyst was in the form of extrudates and was placed inthe reactor and mixed with quartz chips to minimize reactor hot spots.

The hydrocarbon feedstock employed in the following examples was a gasoil having an IBP (Initial Boiling Point) of 332° F., a FBP (FinalBoiling Point) of 853° F. and an API Gravity of 37.9. The feedstockcontained less than 0.1 weight percent total nitrogen. Chemical analysisof the feedstock gave:

    ______________________________________                                                    VOLUME PERCENT                                                    ______________________________________                                        Total Aromatics                                                                             24.7                                                            Mono-aromatics                                                                              19.0                                                            Diaromatics   3.1                                                             Triaromatics  1.2                                                             Tetraaromatics                                                                              0.6                                                             Pentaaromatics                                                                              0.8                                                             Total Saturates                                                                             75.4                                                            ______________________________________                                    

EXAMPLES 1 TO 3

A reference catalyst (Catalyst A) and two catalysts according to thisinvention (Catalyst B and Catalyst C) were prepared as follows. Allweights are on an anhydrous basis unless otherwise designated.

Reference catalyst A was prepared using a zeolitic aluminosilicatedenominated LZ-210. The LZ-210 was prepared according to the disclosureof E.P.C. Publication No. 82,211 and had a SiO₂ to Al₂ O₃ ratio of 9.0,was steamed at 600° C. in 100 percent steam for 1 hour and was ammoniumexchanged by refluxing for 1 hour 1 pound of LZ-210 per pound of NH₄ NO₃(provided as a 10 percent by weight aqueous solution). Catalyst A wasformed into a catalyst by mixing 140 grams of LZ-210 and 60 grams of apseudoboehmite alumina (peptized with 4.2 milliliters of concentratednitric acid in 60 ml. of water) and then mulling the mixture for 10minutes. The mixture was formed into 1/16 inch extrudates, dried at 100°C. for about 10 hours and calcined at 500° C. in air for 2 hours. Thecalcination at 500° C. was carried out in a stepwise manner by heatingthe catalyst to 220° C. over a one hour period, heating the catalyst at220° C. for 1.5 hours, heating the catalyst from 220° C. to 500° C. overa one hour period and then heating the catalyst at 500° C. for 2 hours.The calcined extrudates were pore filled with a Ni(NO₃)₂.6H₂ O andammonium metatungstate solution by mixing and then drying the resultingmixture. The final Catalyst A was prepared to contain the followingweight percent of oxides: 5 percent NiO, 20 percent WO₃, 52.5 percentLZ-210 and 22.5 percent alumina. Chemical analysis of Catalyst A for NiOand WO₃ gave 4.7 weight percent NiO and 20.8 weight percent WO₃.

Catalyst B of the present invention was prepared by employing SAPO-11(which meets the isobutane adsorption criterion described above) andLZ-210 in the formulation of a hydrocracking catalyst. SAPO-11 wasprepared according to example 17 of U.S. Pat. No. 4,440,871 (except thatthe digestion time was 24 hours) and was employed in the as-synthesizedform. The LZ-210 zeolite was the same steamed and ammonium-exchangedLZ-210 employed in Catalyst A. Catalyst B was prepared by mulling 15.0grams of SAPO-11 and 105 grams of the LZ-210 zeolitic aluminosilicateemployed in Catalyst A. A solution containing 42.4 grams of ammoniummetatungstate and 33.93 grams of Ni(NO₃)₂.6H₂ O in 100 cubic centimeters(cc) of water was added to the mixture of SAPO-11 and LZ-210.Pseudobeohmite alumina (30.0 grams peptized by mixing with 4.2milliliter of concentrated nitric acid in 60 milliliters in water) wasadded to the above mixture and the resulting mixture extruded to give1/16 inch extrudates. The extrudates were dried and calcined at 500° C.as described for Catalyst A. Catalyst B was prepared to contain thefollowing weight percent oxides of: 5.0 percent NiO, 20 percent WO₃,52.5 percent LZ-210, 7.5 percent SAPO-11 and 15 percent Al₂ O₃. Chemicalanalysis of Catalyst B for NiO and WO₃ gave 4 weight percent NiO and 16weight percent WO₃.

Catalyst C was prepared by employing SAPO-34 and LZ-210 to formulate thecatalyst. SAPO-34 was prepared according to the procedure described inexamples 32 to 38 of U.S. Pat. No. 4,440,871, and meets the oxygenadsorption criterion described above, but not the isobutane adsorptioncriterion. The LZ-210 was the same LZ-210 employed in the preparation ofCatalyst A. Catalyst C was prepared by mixing 25.08 grams of SAPO-34 and175 grams of LZ-210. The mixture was mulled for fifteen minutes and 53.8grams of the same peptized alumina employed in Catalyst B added. Theresulting mixture was then mixed for fifteen minutes. Water was thenadded to this mixture to form an extrudable mixture and 1/16 inchextrudates formed. The calcined extrudates were pore filled by mixing asolution containing 19.39 grams of Ni(NO₃)₂ 6H₂ O and 24.2 grams ofammonium tungstate in 53 cc of water. The extrudates were then dried andcalcined at 500° C. as described above for Catalyst A. Catalyst C wasprepared to contain the following weight percent of oxides 5 percentNiO; 20 percent WO₃, 52.5 percent LZ-210, 7.5 percent SAPO-34 and 15percent alumina. Chemical analysis of Catalyst C for NiO and WO₃ gave4.99 weight percent NiO and 20.32 weight percent WO₃.

EXAMPLES 4 TO 6

The catalysts prepared in examples 1 to 3 (Catalysts A, B and C) wereevaluated as hydrocracking catalysts according to the above describedprocedure over a series of conversions as set forth below in Tables A, Band C. The products were analyzed and the light gasoline MON (MotorOctane Number) and RON (Research Octane Number) calculated using avolume average of C₅ and C₆ products' blending octane values from theASTM report "Knocking Characterization of Pure Hydrocarbons", TechnicalPublication No. 225 (1958). The MON and RON were calculated using thecompounds measured in the light gasoline fraction and include thefollowing components: 2-methylbutane; n-pentane; 2,3-dimethylpentane;2-methylpentane; 3-methylpentane; n-hexane; methylcyclopentane;2,4-dimethylpentane; cyclohexane; and benzene. The "Conversion" is theweight percent of the feedstock converted to products boiling below 420°F. The following products (as weight percent based on feedstock) arereported in Tables A, B and C: "C₃ "=products containing three carbonatoms; "C₁ to C₄ "=the products containing one to four carbon atoms; "C₅to 185° F."=products containing at least 5 carbon atoms and boilingbelow 185° F.; "185°-420° F.=products boiling from 185° F. to 420° F.;and "C₅ to 420° F."=products containing at least 5 carbon atoms andboiling under 420° F. The C₅, C₆, C₇, C₈ and C₉ products are reportedbelow. The following products were measured in each case: "C₅"=n-pentane and 2-methylbutane; "C₆ "=n-hexane, 2,3-dimethylbutane,2-methylpentane and 3-methylpentane; "C₇ "=n-heptane, 2-methylhexane,3-methylhexane and 2,4-dimethylpentane; "C₈ "=n-octane,2,2,3-trimethylpentane, 2,4-dimethylhexane; 2,3-dimethylhexane,2-methylheptane, 3,4-dimethylhexane and 3-methylheptane; "C₉ "=n-nonane,2,4-dimethylheptane, 2,6-dimethylheptane, 2,5-dimethylheptane,4-methyloctane, 2-methyloctane and 3-methyloctane. These components ofthe gasoline products were determined by capillary gas chromatography.The quantities of light and heavy gasoline products and unconverted feedwere determined by the simulated distillation described in ASTM testmethod 2887.

                                      TABLE A                                     __________________________________________________________________________    (Catalyst A)                                                                  Experi-                                                                       ment                                                                          No. Conv.                                                                             C.sub.1 -C.sub.4                                                                  C.sub.3                                                                          C.sub.5 -185° F.                                                             185-420° F.                                                                  RON MON i/n-C.sub.5                                                                       n-C.sub.5                                                                        i-C.sub.5                                                                        i/n-C.sub.6                                                                       n-C.sub.6                                                                        i-C.sub.6                                                                        n-C.sub.7              __________________________________________________________________________    1   42.12                                                                             3.85                                                                              0.34                                                                             4.20  33.09 85.78                                                                             85.17                                                                             3.08                                                                              0.40                                                                             1.23                                                                             4.79                                                                              0.29                                                                             1.41                                                                             0.567                  2   41.47                                                                             3.91                                                                              0.34                                                                             4.15  33.28 85.91                                                                             85.31                                                                             3.12                                                                              0.40                                                                             1.23                                                                             4.88                                                                              0.29                                                                             1.40                                                                             0.586                  3   46.46                                                                             4.50                                                                              0.41                                                                             5.26  36.21 85.90                                                                             85.46                                                                             3.13                                                                              0.51                                                                             1.60                                                                             4.99                                                                              0.36                                                                             1.77                                                                             0.687                  4   46.40                                                                             4.40                                                                              0.41                                                                             5.38  36.09 85.82                                                                             85.27                                                                             3.13                                                                              0.51                                                                             1.61                                                                             5.00                                                                              0.37                                                                             1.84                                                                             0.593                  5   49.39                                                                             4.94                                                                              0.48                                                                             6.23  37.79 85.87                                                                             85.37                                                                             3.15                                                                              0.60                                                                             1.89                                                                             5.15                                                                              0.42                                                                             2.15                                                                             0.741                  6   49.50                                                                             5.07                                                                              0.50                                                                             6.41  37.68 85.85                                                                             84.76                                                                             3.20                                                                              0.60                                                                             1.93                                                                             5.15                                                                              0.43                                                                             2.23                                                                             0.608                  __________________________________________________________________________                        Experi-                                                                       ment                          Hours on                                        No. i-C.sub.7                                                                        i/n-C.sub.7                                                                      n-C.sub.8                                                                        i-C.sub.8                                                                        i/n-C.sub.8                                                                       n-C.sub.9                                                                        i-C.sub.9                                                                        i/n-C.sub.9                                                                       Stream                                                                             (°F.)           __________________________________________________________________________                        1   3.70                                                                             6.53                                                                             0.428                                                                            4.29                                                                             10.02                                                                             0.424                                                                            3.80                                                                             8.97                                                                              68   686                                        2   3.91                                                                             6.66                                                                             0.415                                                                            4.59                                                                             11.06                                                                             0.431                                                                            3.98                                                                             9.23                                                                              93   687                                        3   4.75                                                                             6.91                                                                             0.485                                                                            6.34                                                                             13.06                                                                             0.446                                                                            4.29                                                                             9.63                                                                              118  692                                        4   4.05                                                                             6.83                                                                             0.454                                                                            5.60                                                                             12.33                                                                             0.428                                                                            4.03                                                                             9.42                                                                              141  961                                        5   5.26                                                                             7.10                                                                             0.540                                                                            6.91                                                                             12.79                                                                             0.482                                                                            4.84                                                                             10.03                                                                             164  695                                        6   64.31                                                                            7.09                                                                             0.471                                                                            5.89                                                                             12.50                                                                             0.455                                                                            4.27                                                                             9.37                                                                              188  695                    __________________________________________________________________________

                                      TABLE B                                     __________________________________________________________________________    (Catalyst B)                                                                  Experi-                                                                       ment                                                                          No. Conv.                                                                             C.sub.1 -C.sub.4                                                                  C.sub.3                                                                          C.sub.5 -185° F.                                                             185-420° F.                                                                  RON MON i/n-C.sub.5                                                                       n-C.sub.5                                                                        i-C.sub.5                                                                        i/n-C.sub.6                                                                       n-C.sub.6                                                                        i-C.sub.6                                                                        n-C.sub.7              __________________________________________________________________________    1   38.83                                                                             3.69                                                                              0.31                                                                             3.79  31.03 86.58                                                                             85.96                                                                             3.38                                                                              0.34                                                                             1.15                                                                             5.68                                                                              0.23                                                                             1.31                                                                             0.417                  2   39.38                                                                             3.90                                                                              0.33                                                                             3.76  31.55 86.61                                                                             85.95                                                                             3.37                                                                              0.34                                                                             1.13                                                                             5.75                                                                              0.23                                                                             1.30                                                                             0.451                  3   43.55                                                                             3.32                                                                              0.39                                                                             4.89  33.82 87.10                                                                             86.50                                                                             3.67                                                                              0.41                                                                             1.52                                                                             6.51                                                                              0.27                                                                             1.74                                                                             0.420                  4   48.47                                                                             4.70                                                                              0.48                                                                             5.55  37.79 87.01                                                                             86.47                                                                             3.68                                                                              0.48                                                                             1.75                                                                             6.46                                                                              0.31                                                                             1.97                                                                             0.484                  5   66.99                                                                             7.18                                                                              0.73                                                                             10.41 48.32 87.33                                                                             86.87                                                                             4.04                                                                              0.85                                                                             3.42                                                                             7.10                                                                              0.53                                                                             3.80                                                                             0.561                  6   67.84                                                                             7.14                                                                              0.81                                                                             9.73  49.98 87.39                                                                             86.92                                                                             4.08                                                                              0.78                                                                             3.19                                                                             7.27                                                                              0.49                                                                             3.57                                                                             0.553                  __________________________________________________________________________                       Experi-                                                                       ment                           Hours on                                       No. i-C.sub.7                                                                        i/n-C.sub. 7                                                                      n-C.sub.8                                                                        i-C.sub.8                                                                        i/n-C.sub.8                                                                       n-C.sub.9                                                                        i-C.sub.9                                                                        i/n-C.sub.9                                                                       Stream                                                                             (°F.)           __________________________________________________________________________                       1   3.41                                                                             8.18                                                                              0.295                                                                            4.76                                                                             16.14                                                                             0.335                                                                            3.54                                                                             10.58                                                                             68   686                                       2   3.73                                                                             8.27                                                                              0.327                                                                            5.20                                                                             15.90                                                                             0.357                                                                            3.84                                                                             10.75                                                                             92   685                                       3   4.01                                                                             9.55                                                                              0.297                                                                            5.04                                                                             16.98                                                                             0.327                                                                            3.85                                                                             11.78                                                                             140  692                                       4   4.52                                                                             9.34                                                                              0.362                                                                            5.93                                                                             16.38                                                                             0.358                                                                            4.13                                                                             11.55                                                                             165  696                    __________________________________________________________________________

                                      TABLE C                                     __________________________________________________________________________    (Catalyst C)                                                                  Experi-                                                                       ment                                                                          No. Conv.                                                                             C.sub.1 -C.sub.4                                                                  C.sub.3                                                                          C.sub.5 -185° F.                                                             185-420° F.                                                                  RON MON                                                                              i/n-C.sub.5                                                                       n-C.sub.5                                                                         i-C.sub.5                                                                        i/n-C.sub.6                                                                       n-C.sub.6                                                                        i-C.sub.6                                                                         Stream                                                                            (°F.)      __________________________________________________________________________    1   37.89                                                                             0.35                                                                              3.72                                                                             3.37  30.73 86.94                                                                             85.5                                                                             3.44                                                                              0.29                                                                              1.01                                                                             5.97                                                                              0.19                                                                             1.16                                                                              64  686               2   38.18                                                                             0.32                                                                              3.62                                                                             3.53  30.58 86.96                                                                             85.1                                                                             3.48                                                                              0.32                                                                              1.10                                                                             6.14                                                                              0.20                                                                             1.22                                                                              86  686               3   41.18                                                                             0.38                                                                              3.71                                                                             4.29  31.98 87.09                                                                             86.5                                                                             3.52                                                                              0.37                                                                              1.35                                                                             6.69                                                                              0.23                                                                             1.54                                                                              110 690               4   48.30                                                                             0.46                                                                              4.19                                                                             4.91  30.64 87.23                                                                             86.76                                                                            3.75                                                                              0.42                                                                              1.59                                                                             7.06                                                                              0.25                                                                             1.78                                                                              138 695               5   43.70                                                                             0.46                                                                              4.53                                                                             5.45  33.12 87.13                                                                             86.55                                                                            3.72                                                                              0.47                                                                              1.74                                                                             6.85                                                                              0.29                                                                             1.97                                                                              160 695               6   49.41                                                                             0.60                                                                              5.25                                                                             6.56  36.69 87.40                                                                             86.89                                                                            3.93                                                                              0.54                                                                              2.13                                                                             7.24                                                                              0.33                                                                             2.39                                                                              184 703               7   49.80                                                                             0.59                                                                              5.39                                                                             7.00  36.68 87.42                                                                             86.63                                                                            4.00                                                                              0.56                                                                              2.24                                                                             7.36                                                                              0.35                                                                             2.58                                                                              208 703               8   50.41                                                                             0.81                                                                              5.58                                                                             7.43  36.24 87.13                                                                             86.23                                                                            4.03                                                                              0.53                                                                              2.15                                                                             7.38                                                                              0.39                                                                             2.89                                                                              231 709               __________________________________________________________________________

Comparison of the product distribution obtained using Catalyst A andthose obtained using Catalysts B and C demonstrate the improved octanenumber of the light gasoline fraction (C₅ to 185° F.) obtained using thecatalyst of this invention when compared at similar conversion. Further,the C₅ and C₆ hydrocarbon iso/normal ratio increased for Catalysts B andC. Since iso-alkanes have higher octane numbers, the product obtained byuse of Catalysts B and C have improved calculated octane numbers.

The data in Tables A, B and C are graphically depicted in FIGS. 1 to 13and demonstrate the benefits obtained by use of the catalysts of theinstant invention in hydrocracking processes. FIGS. 1 and 2 show acomparison between Catalysts A, B and C of the light gasoline yield (C₅-185° F.) as a function of conversion. Catalysts B and C producedsimilar or higher yields of the light gasoline product as compared tothat obtained by use of reference Catalyst A. FIGS. 3 and 4 compare thecalculated RON (Research Octane Number) of the light gasoline fractionsobtained by use of Catalyst A, B and C. Catalysts B and C produced lightgasoline fractions having higher RON values as compared to the lightgasoline fractions produced by use of Catalyst A. FIG. 5 compares theyield of the heavy gasoline fraction (C₅ to 420° F.) as a function ofconversion for Catalyst A and C and shows that the reference catalystproduced more heavy gasoline product. FIG. 6 compares yield of the heavygasoline fraction as a function of conversion for Catalysts A andCatalyst B. Surprisingly, the yield of the heavy gasoline fraction issimilar to reference Catalyst A while the RON of the light gasolinefraction is improved with Catalyst B. FIGS. 7, 8, 9 and 10 compare theiso to normal ratios of the C₅ and C₆ hydrocarbons produced by use ofCatalysts A, B and C. In each of these cases, Catalysts B and C producedproducts having a higher iso to normal ratios than the products producedby use of Catalyst A. FIG. 11 compares the iso to normal ratio of theC₅, C₆, C₇, C₈ and C₉ hydrocarbons as a function of carbon number forCatalyst A and Catalyst B. The products obtained using Catalyst B showeda higher iso to normal ratio for C₅, C₆, C₇, C₈ and C₉ hydrocarbons,thus indicating higher octane products. FIGS. 12 and 13 show the yieldof C₃ products as a function of conversion for Catalysts A, B and C.Catalyst C showed a slight increase in C₃ products, as compared toCatalyst A, while Catalyst B was similar to Catalyst A in the yield ofC₃ products.

Thus, the above results demonstrate that the RON of the light gasolinefraction was improved by use of Catalyst B and Catalyst C and the iso tonormal ratiio of C₅ to C₉ products increased while the yield of thelight gasoline and heavy gasoline fractions remained substantiallyunchanged or increased. Thus the octane number of the light gasolinefraction obtained using the SAPO-containing catalyst was increasedrelative to the same catalyst but without a SAPO component. The resultsalso indicate that Catalyst B (containing SAPO-11) was superior toCatalyst C (containing SAPO-34) in its improvement of the octane numberof the light gasoline products without a gasoline yield loss. SAPO-11 ischaracterized by the above discussed adsorption of isobutane whileSAPO-34 is not and, accordingly, SAPO-11 is in the preferred class ofNZ-MSs employed in this invention.

EXAMPLE 7

A catalyst was prepared employing SAPO-11 alone to investigate thehydrocracking functionality of the non-zeolitic molecular sieves used inthe catalysts of this invention. SAPO-11 was prepared according to theprocedure described in Example 18 of U.S. Pat. No. 4,440,871, except thefinal molar ratio of di-n-propylamine to Al₂ O₃ was 1.0 to 1. Thecatalyst was prepared by mixing 150 grams of SAPO-11 with 100 grams ofKaiser medium density alumina and a sufficient amount of water to forman extrudate mixture (paste). The mixture was extruded into 1/16 inchextrudates and dried in air at 100° C. for 16 hours. The extrudates werethen calcined in air at 480° C. for 2 hours. The extrudates (153 gram)were then mixed (pore filled) with 150 cc of an aqueous solutioncontaining 40.0 grams of nickel nitrate hexahydrate and 48.8 grams ofammonium metatungstate. The mixture was then dried for 16 hours at 100°C. and then calcined in air at 480° C. for 2 hours. The catalyst wasprepared to contain, given as the weight percent oxide: 5 weight percentNiO; 23 weight percent WO₃ ; 36 weight percent SAPO-11; and 36 percentAl₂ O₃. Chemical analysis for NiO and WO₃ gave 5.4 weight percent NiOand 23.0 weight percent WO₃.

The catalyst was evaluated by contacting a selected feedstock withhydrogen at a total pressure of 2000 psig at a Liquid Hourly SpaceVelocity (LHSV) of one and a hydrogen flow rate of 10,000 SCFB (StandardCubic Feed per Barrel) at temperatures between about 700° F. and 840° F.Products boiling below 600° F. were collected and evaluated and theconversion given based on these products. The feedstock employed in thisexample was a vacuum gas oil having an IBP (Initial Boiling Point) of560° F. and a FBP (Final Boiling Point) of 1148° F. (both determined byASTM test method D-2887), API Gravity of 22.3 and having a pour point ofgreater than 95° F. The feedstock was characterized by the followingphysical and chemical characteristics:

    ______________________________________                                                      Weight Percent                                                  ______________________________________                                        Mono-naphthenes 24.1                                                          Poly-naphthenes 9.5                                                           Mono-aromatics  13.3                                                          Di-aromatics    9.3                                                           Tri-aromatics   4.3                                                           Tetra-aromatics 2.7                                                           Penta-aromatics 0.7                                                           ______________________________________                                    

The reactor effluents were collected and the fraction of the feed(weight basis) converted to products boiling below 600° F. determined bysimulated distillation. The conversion is reported as the weight percentof feedstock converted to products boiling below 600° F. The pour pointswere determined according to ASTM test method D-97-66 on the reactoreffluent after maintaining the effluent at about 130° F. during itscollection.

The conversion and pour point were as follows:

    ______________________________________                                        Temperature (°F.)                                                                     Conversion                                                                              Pour Point (°F.)                              ______________________________________                                        700            7.52      85                                                   724            9.84      80                                                   749            17.95     70                                                   769            30.06     55                                                   788            41.60     25                                                   797            36.64     35                                                   788            29.89     40                                                   788            33.74     45                                                   807            43.64     30                                                   821            45.12     30                                                   822            45.50     30                                                   840            56.88     20                                                   ______________________________________                                    

The above data demonstrate the conversion of the higher boilingfeedstock to lower boiling products in the presence of hydrogen and thatsuch products are characterized by a lower pour point than the initialfeedstock. It is apparent from the above data that very hightemperatures must be employed to obtain significant conversion of aheavy feed using a catalyast containing SAPO-11 alone as a non-zeoliticmolecular sieve, with a metal hydrogenation component but without acracking component such as a zeolite.

What is claimed is:
 1. A hydrocracking process for processing crude oilfeedstock in the presence of hydrogen comprising contacting in thepresence of hydrogen at conditions effective to hydrocrack a crude oilfeedstock with a hydrocracking catalyst comprising an amount of at leastone metal hydrogenation catalyst effective to provide a hydrogenationfunction and an amount of at least one non-zeolitic molecular sievecharacterized in its calcined form by an adsorption of isobutane of atleast 2 percent by weight at a partial pressure of 500 torr and atemperature of 20° wherein a hydrocracked product is formed.
 2. Theprocess of claim 1 wherein the amount of said non-zeolitic molecularsieve is effective to produce an increased octane number in a lightgasoline fraction of the hydrocracked product.
 3. The process of claim 1wherein said non-zeolitic molecular sieve is further characterized inits calcined form by an adsorption of triethylamine of from zero to lessthan 5 percent by weight at a pressure of 2.6 torr and a temperature of22° C.
 4. The process of claim 3 wherein said adsorption oftriethylamine is less than 3 percent by weight.
 5. The hydrocrackingprocess of claim 1 wherein said hydrocracking catalyst contains aneffective amount of at least one traditional hydrocracking component(THC) comprising a zeolitic aluminosilicate having activity in ahydrocracking process, said THC being present in a weight ratio betweenabout 1:10 and about 500:1 of said THC to said non-zeolitic molecularsieve and from 0 to about 99 weight percent of at least one inorganicoxide matrix component, based on the total weight of said hydrocrackingcatalyst.
 6. The process of claim 5 wherein the amount of said zeolitealuminosilicate is effective to convert said feedstock to lowermolecular weight products.
 7. The process of claim 5 wherein the weightratio of THC to said non-zeolitic molecular sieve is between about 1:2and about 50:1.
 8. The process of claim 7 wherein the weight ratio ofTHC to said non-zeolitic molecular sieve is between about 1:1 and about20:1.
 9. The process of claim 5 wherein said inorganic oxide componentis present in an amount between about 5 and about 95 percent by weight,based on the total weight of said catalyst.
 10. The process according toclaim 5 wherein at least one of said non-zeolitic molecular sieve andsaid zeolitic aluminosilicate contains an effective amount of a cationselected from the group consisting of ammonium, Group IIA, Group IIIA,Groups IIIB to VIIB, cerium, lanthanum, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, lutetium and mixtures thereof. 11.The process of claim 1 wherein said at least one non-zeolitic molecularsieve is selected from the group consisting of SAPO, ELAPSO, ELAPO,MeAPO, FeAPO and TiAPO molecular sieves, and mixtures thereof.
 12. Theprocess of claim 1 wherein said at least one non-zeolitic molecularsieve contains at least three framework elements as tetrahedral oxides.13. The process of claim 1 wherein said non-zeolitic molecular sieve hasat least part of its cations as hydrogen-forming species.
 14. Theprocess of claim 13 wherein said hydrogen-forming species is NH₄ ⁺ orH⁺.
 15. The process of claim 10 wherein said zeolitic aluminosilicatecontains between about 0.1 percent and about 20 weight percent of saidcations.
 16. The process of claim 5 wherein said inorganic oxide matrixcomponent is selected from the group consisting of clays, silicas,aluminas, silica-aluminas, silica-zirconias, silica-magnesia,alumina-borias, alumina-titanias and mixtures thereof.
 17. The processof claim 1 wherein said non-zeolitic molecular sieve is selected fromthe group consisting of CoAPSOs, FeAPSOs, MgAPSOs, MnAPSOs, TiAPSOs,ZnAPSOs, CoMgAPSOs, CoMnMgAPSOs, MeAPOs, TiAPOs, FeAPOs, ELAPOs andmixture thereof.
 18. The process of claim 1 wherein said non-zeoliticmolecular sieve is selected from the group consisting of CoAPSOs,FeAPSOs, MgAPSOs, MnAPSOs, TiAPSOs, ZnAPSOs, CoMgAPSOs, CoMnMgAPSOs andmixtures thereof.
 19. The process of claim 1 wherein said non-zeoliticmolecular sieve is selected from the group consisting of ELAPSO-5,ELAPSO-11, ELAPSO-31, ELAPSO-37, ELAPSO-40, ELAPSO-41 and mixturesthereof.
 20. The process of claim 19 wherein said non-zeolitic molecularsieve is selected from the group consisting of CoAPSO-11, CoAPSO-31,FeAPSO-11, FeAPSO-31, MgAPSO-11, MgAPSO-31, MnAPSO-11, MnAPSO-31,TiAPSO-11, ZnAPSO-11, ZnAPSO-31, CoMgAPSO-11, CoMnMgAPSO-11 and mixturesthereof.
 21. The process of claim 1 wherein said non-zeolitic molecularsieve is selected from the group consisting of MeAPO-11, TiAPO-11,TiAPO-31, FeAPO-11, ELAPO-11, ELAPO-31, ELAPO-40 and mixtures thereof.22. The process of claim 21 wherein "Me" is selected from the groupconsisting of cobalt, magnesium, manganese, zinc and mixtures thereof.23. The process of claim 21 wherein "Me" is selected from the groupconsisting of magnesium, manganese and mixtures thereof.
 24. The processof claim 1 wherein said feedstock is selected from the group consistingof distillate gas oils, atmospheric residual oils, vacuum residual oils,syncrudes and mixtures thereof.
 25. The process of claim 5 wherein saidzeolitic aluminosilicate is selected from the group consisting ofzeolite Y, ultrastable Y, zeolite X, zeolite beta, zeolite KZ-20,faujasite, LZ-210, LZ-10, ZSM zeolites and mixtures thereof.
 26. Theprocess of claim 25 wherein said ZSM zeolite is selected from the groupconsisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.27. The process of claim 25 wherein said ZSM zeolite has a pentasilstructure.
 28. The process of claim 5 wherein said zeoliticaluminosilicate is selected from the group consisting of zeolite Y,ultrastable Y, zeolite X, zeolite beta, zeolite KZ-20, faujasite,LZ-210, LZ-10 and mixtures thereof.
 29. The process of claim 5 whereinsaid zeolitic aluminosilicate is selected from the group consisting ofzeolite Y, ultrastable Y, zeolite X, zeolite beta, zeolite KZ-20,LZ-210, LZ-10, ZSM-type zeolites selected from the group consisting ofZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48, and mixturesthereof.
 30. The process of claim 1 wherein said hydrogenation metalcatalyst is at least one metal selected from the group consisting of Pt,Pd, Rh, Ru, Ni, W, Mo, Co, Cr and mixtures thereof.
 31. The process ofclaim 30 wherein said metal is selected from the group consisting of Pt,Pd, Rh, Ru and mixtures thereof and is present in an amount betweenabout 0.05 weight percent and about 1.5 weight percent, based on thetotal weight of said hydrocracking catalyst.
 32. The process of claim 30wherein the metal is selected from the group consisting of Ni, W, Mo,Co, Cr and mixtures thereof and is present in an amount between about1.0 and about 30 percent by weight, based on the total weight of saidhydrocracking catalyst.
 33. The process of claim 1 wherein the processis carried out by contacting a crude oil feedstock boiling between 400°F. and about 1200° F. in the presence of an effective amount of hydrogenwith said conversion catalyst at a temperature between about 400° F. andabout 1600° F., at a pressure between about 300 psig to about 5000 psig.34. The process of claim 5 wherein the process is carried out bycontacting a crude oil feedstock boiling between 400° F. and about 1200°F. in the presence of an effective amount of hydrogen with saidconversion catalyst at a temperature between about 400° F. and about1600° F., at a pressure between about 300 psig to about 5000 psig. 35.The process of claim 33, wherein said process is carried out ateffective hydrocracking conditions upon a hydrocarbon feed which boilsbetween about 400° F. and about 900° F., wherein the hydrogen to feedratio is at least 1000 standard cubic feed of hydrogen per barrel offeed (SCFB), the total process pressure is between about 400 and about4000 psig, the temperature is between about 450° F. and 800° F. and theliquid hourly space velocity is between 0.2 and
 5. 36. The process ofclaim 35 wherein the feed has been subjected to hydrodenitrification bypre-treatment in a hydrotreater.
 37. The process of claim 36 wherein thefeed has been subjected to hydrodesulfurization by pre-treatment in ahydrotreater.
 38. The process of claim 35 wherein the hydrocarbon feedboils between about 400° F. and 800° F.
 39. The process of claim 1wherein the hydrocarbon feed boils between about 400° F. and 900° F. 40.The process of claim 39 wherein the hydrocarbon feed has been pretreatedin a hydrotreater to reduce the content of sulfur and nitrogencompounds.
 41. In a hydrocracking process for processing a crude oilfeedstock in the presence of hydrogen and a hydrocracking catalyst theimprovement comprising contacting the crude oil feedstock at conditionseffective to hydrocrack and in the presence of hydrogen with ahydrocracking catalyst comprising an amount of a metal hydrogenationcatalyst effective to provide a hydrogenation function and an amount ofat least one non-zeolitic molecular sieve characterized in its calcinedform by an adsorption of isobutane of at least 2 percent by weight at apartial pressure of 500 torr and a temperature of 20° C. effective toincrease the octane number of said light gasoline fraction.
 42. Theprocess of claim 41 wherein said non-zeolitic molecular sieve is furthercharacterized in its calcined form by an adsorption of triethylaminefrom zero to less than 5 percent by weight at a pressure of 2.6 torr anda temperature of 22° C.
 43. The process of claim 42 wherein saidadsorption of triethylamine is less than 3 percent by weight.
 44. Theprocess of claim 41 wherein the process is carried out by contacting acrude oil feedstock boiling between 400° F. and about 1200° F. in thepresence of an effective amount of hydrogen with said conversioncatalyst at a temperature between about 400° F. and about 1600° F., at apressure between about 300 psig to about 5000 psig.
 45. Thehydrocracking process of claim 41 wherein said hydrocracking catalystcontains an effective amount of at least one traditional hydrocrackingcomponent (THC) comprising a zeolitic aluminosilicate having activity ina hydrocracking process, said THC being present in a weight ratiobetween about 1:10 and about 500:1 of said THC to said non-zeoliticmolecular sieves and from 0 and about 99 weight percent of at least oneinorganic oxide matrix component, based on the total weight of saidcatalyst.
 46. A hydrocracking process for processing a crude oilfeedstock in the presence of hydrogen, comprising contacting, in thepresence of hydrogen at conditions effective to hydrocrack, a crude oilfeedstock with a hydrocracking catalyst comprising an amount of at leastone metal hydrogenation catalyst effective to provide a hydrogenationfunction, an amount of at least one traditional hydrocracking component(THC) comprising a zeolitic aluminosilicate having activity in ahydrocracking process effective to produce hydrocracking, and at leastone non-zeolitic molecular sieve selected from the group consisting ofSAPO, ELAPSO, ELAPO, MeAPO, FeAPO and TiAPO molecular sieves, which ischaracterized in its calcined form by an adsorption of isobutane of atleast 2 percent by weight at a partial pressure of 500 torr and atemperature of 20° C., said THC being present in a weight ratio betweenabout 1:10 and about 500:1 of said THC to said non-zeolitic molecularsieve, and from 0 to about 99 weight percent of at least one inorganicoxide matrix component, based upon the total weight of saidhydrocracking catalyst, wherein said non-zeolitic molecular sieve ispresent in an amount effective to produce a different productdistribution than obtained from the use of said hydrocracking catalystwithout said non-zeolitic molecular sieve.
 47. The hydrocracking processof claim 46 wherein said non-zeolitic molecular sieve is furthercharacterized in its calcined form by an adsorption of triethylamine offrom zero to less than 5 percent by weight at a pressure of 2.6 torr anda temperature of 22° C.
 48. The process of claim 46 wherein at least oneof said non-zeolitic molecular sieve and said zeolitic aluminosilicatecontains an effective amount of a cation selected from the groupconsisting of ammonium, Group IIA, Group IIIA, Groups IIIB to VIIB,cerium, lanthanum, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, lutetium and mixtures thereof.
 49. The process of claim 46wherein said zeolitic aluminosilicate is selected from the groupconsisting of zeolite Y, ultrastable Y, zeolite X, zeolite, beta,zeolite KZ-20, faujasite, LZ-210, LZ-10, ZSM-5, ZSM-11, ZSM-12, ZSM-23,ZSM-35, ZSM-38, ZSM-48 and mixtures thereof.
 50. The process of claim 46wherein said hydrogenation metal catalyst is at least one metal selectedfrom the group consisting of Pt, Pd, Rh, Ru, Ni, W, Mo, Co and Cr, andmixtures thereof.
 51. The process of claim 46 wherein the amount of saidzeolitic aluminosilicate is effective to convert said feedstock to lowermolecular weight products and the amount of said non-zeolitic molecularsieve is effective to produce an increased octane number in a lightgasoline fraction of the product.